BRPI0606968B1 - process for cross-linking polymer and cross-linked polymer - Google Patents

Abstract

A process for producing crosslinked polymer comprising low yield silane crosslinking agent and the resulting crosslinked polymer. A polymer cross-linking process employing a silane crosslinking agent which upon hydrolysis produces a small amount of volatile organic compound.

Description

"PROCESS FOR RECYCLING POLYMER AND RETICULATED POLYMER" CROSS-RELATED APPLICATION REFERENCE

The present invention claims the priority of Provisional Application US 60 / 651,112 filed February 8, 2005, the contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

The use of alkoxy-functional silane for polymer crosslinking, especially for the production of tubing, foams, wires and cables, and heat shrinkable tubing, results in the release of alcohol by silane hydrolysis. This alcohol is typically methanol or ethanol, and can cause environmental, health and safety problems. As emissions of volatile organic compounds (VOCs) become more tightly regulated, pipe, foam, tube, wire and cable formulators and producers are often forced to reduce production, install recovery or repair equipment, or use controls. engineered to meet new stricter emission limits as well as reduce the risk of explosion and flammability. As an example, potable water pipe manufacturers are facing increasing limitations on the methanol content allowed in pipes as produced. These manufacturers need a more cost-effective way to reduce the presence and emission of VOCs from their conventional silane processes.

[003] Silanes are commonly used as crosslinkers for the production of PEX-b (silane crosslinked polyethylene) tubing, cable coatings, low and medium voltage insulating jacketing, insulation foams, heat shrinkable products such as as a tube. Silane is typically used in conjunction with a peroxide, which is used to graft the silane into the crosslinked polymer. Other additives such as antioxidants, metal deactivators, condensation catalysts and so on may also be included.

[004] The most commonly employed silanes are vinyl functional silanes, where vinyltrimethoxy silane is the most prevalent. Production of crosslinked polymers involves grafting silane on the polymer and silane hydrolysis and condensation to provide crosslinked polymers. The graft reaction is typically performed on a single screw extruder, while the hydrolysis / condensation reaction may be performed under various conditions, including exposure to moisture under ambient conditions, exposure to hot water via grafted resin submergence, or vapor exposure. of water. In the production of drinking water pipes, for example, hot water is circulated through the extruded pipe to complete crosslinking. Circulating hot water for an extended period also helps remove the methanol byproduct that is wanted during crosslinking. Water must circulate through the pipelines until methanol levels have decreased to permissible limits.

Cross-linking of silane polymers can result in many improvements in chemical resistance, abrasion resistance, high temperature creep resistance, wet and dry electrical properties, scratch resistance, tensile strength, flexural strength. , deformation, tensile failure properties, memory effect, impact resistance, aging resistance, reduced drip phenomenon, and other mechanical properties.

BRIEF DESCRIPTION OF THE INVENTION

In accordance with the present invention there is provided a process for cross-linking a polymer comprising: a) introducing into the structure of the thermoplastic polymer to be cross-linked, under substantially anhydrous conditions, a silane which upon hydrolysis of its hydrolysing sites; yields a reduced amount of volatile organic compound compared to that produced by hydrolysis of a silane having an equivalent number, per mol, of hydrolysable sites, all of which are hydrolysable alkoxy groups; and b) cross-linking the polymer by exposing the polymer to hydrolysis / condensation conditions, optionally in the presence of a hydrolysis / condensation catalyst.

[007] The present invention also includes the crosslinked polymer resulting from the above cross-linking process and products manufactured therefrom.

The silane employed in the process of this invention provides crosslinking in a similar manner to silane previously used for polymer crosslinking, but has the advantage of not producing a significant amount of VOCs with consequent benefits to health and safety problems in the environment. Work In addition, the silane used in the present invention reduces the need to recover and repair equipment and the use of special engineering controls to comply with new stricter emission limits as well as reduce the risk of explosion, flammability and health. Therefore, the use of silane in the process of the present invention results in significant economic benefits as well as in comparison with known polymer crosslinking processes utilizing VOC-producing silane.

[009] The term "volatile organic compound" (VOC) as used herein is to be understood to apply to, and designate, substantially pure organic compounds that are volatile by the Environmental Protection Agency (EPA) Method 24 for the USA. or which do not meet the specific criteria established for European countries with respect to vapor pressure or boiling point or are cited as VOCs in the European Union Directive 2004/42 / EC. Specific examples for such VOCs include methanol, ethanol, propanol, isopropanol, acetoxysilanes, etc.

Various other features, aspects and advantages of the present invention will become more apparent with reference to the following description and the appended claims.

BRIEF DESCRIPTION OF DRAWINGS

Figure 1 is a graph illustrating the percent gel content of Examples 23-30 and Comparative Examples 11-14.

[Ο 012] Figure 2 is a graph illustrating the tensile stress at break of Examples 23 to 30 and Comparative Examples 11 to 14.

Figure 3 is a graph illustrating the percentage of elongation at break of Examples 23 to 30 and Comparative Examples 11 to 14.

DETAILED DESCRIPTION OF THE INVENTION

A process for crosslinking a polymer is provided which comprises: a) introducing into the structure of the thermoplastic polymer to be crosslinked, under substantially anhydrous conditions, a silane, which upon hydrolysis of its hydrolysable sites yields a reduced amount of volatile organic compound compared to water-based produced by hydrolysis of a silane having an equivalent number of hydrolysable sites, all of which are hydrolysable alkoxy groups; and b) cross-linking the polymer by exposing the polymer to silane hydrolysis conditions, optionally in the presence of a hydrolysis / condensation catalyst.

The thermoplastic polymer to be crosslinked may be a monomer of vinyl, olefin, acrylate, methacrylate, etc. or combinations of such monomers.

The terms "lower someone" and "lower someone" mean to include, in a first embodiment, a carbon chain having from 2 to 20 carbon atoms, in a second embodiment, a carbon chain having from 2 to 10 atoms of carbon, in a third embodiment, a carbon chain having from 2 to 8 carbon atoms.

The polymer to be crosslinked may be a homopolymer such as polyethylene, polypropylene, polybutadiene, low density polyethylene, high density polyethylene, linear low density polyethylene, polyvinyl chloride, polyvinyl chloride ), chlorinated polyethylene, and the like, or a copolymer such as those derived from two or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, etc.

According to another embodiment, the polymer to be cross-linked is at least one copolymer selected from the group consisting of (i) ethylene copolymerized with one or more other ethylenically unsaturated monomer such as alpha-olefin of 3 to 10 atoms. ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid ester and ethylenically unsaturated dicarboxylic acid anhydride, (ii) olefin-based rubber such as ethylene propylene (EP) rubber, ethylene-propylene-monomer rubber diene (EPDM) and styrene butadiene rubber (SBR) and (III) ionomer resin, for example any of those described in US Patent 4,303,573, the entire contents of which are incorporated herein by reference.

Copolymerizable unsaturated carboxylic acids and anhydrides thereof include acrylic acid, methacrylic acid, butenoic acid, maleic acid, maleic anhydride, and the like.

Copolymerizable ethylenically unsaturated carboxylic acid esters include vinyl acetate, vinyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and butyl methacrylate.

Specific copolymers include those of ethylene propylene, ethylene butene, ethylene hexene, ethylene octene, ethylene vinyl acetate, ethylene methyl methacrylate, ethylene acrylate, ethylene butyl acrylate, ethylene propylene diene elastomers, styrene butadiene, etc.

According to another embodiment, the polymers to be crosslinked may be a mixture of two or more such polymers. Thus, for example, a polyethylene may be mixed with any polymer compatible with it, such as polypropylene, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, polyvinyl chloride, styrene / butadiene copolymer, vinyl acetate copolymer. -la / ethylene, acrylonitrile / butadiene copolymer and vinyl chloride / vinyl acetate copolymer.

According to another embodiment, the polymer may be a mixture of polymers comprising at least one polyolefin elastomer component and at least one crystalline component. The polyolefin elastomer component of the mixture may be an ethylene and alpha olefin copolymer or ethylene, alpha olefin and diene terpolymer. If the former, then preferably the copolymers used comprise from about 35 to about 95% by weight (wt%) of ethylene, and about 5 to about 65% by weight of at least one alpha olefin comonomer. In another embodiment, the copolymers comprise from 25 to 65% by weight of at least one alpha olefin comonomer. Comonomer content is measured using infrared spectroscopy according to Method B ASTM D-2238. Typically, linear ethylene polymers are ethylene copolymers and an alpha-olefin of 3 to about 20 carbon atoms (e.g. propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene 1-octene, styrene, etc.) according to another embodiment, from 3 to 10 carbon atoms, and according to another embodiment an ethylene and 1-octene copolymer.

Ethylene / alpha-olefin copolymers can be either heterogeneously branched or homogeneously branched. These heterogeneously branched copolymers, that is polyethylenes, fall into two broad categories, those prepared with a high temperature and high pressure free radical generator, and those prepared with a coordinating catalyst, at high temperature and relatively low pressure. The former are generally known as low density polyethylene (LDPE) and are characterized by branched chains of polymerized monomeric units pendant from the polymer backbone. According to one embodiment of the present invention, the elastomer component is LDPE having a density of less than about 0.885 g / cm3.

Ethylene copolymers and copolymers prepared by the use of a coordinating catalyst, such as Ziegler or Phillips catalyst, are generally known as linear polymers due to the substantial absence of branching chains of pendant main chain polymerized monomer units . High density polyethylene (HDPE), generally having a density of about 0.941 to about 0.965 g / cm3, is typically an ethylene homopolymer, and it contains relatively few branch chains relative to the various linear ethylene copolymers and a alpha olefin. HDPE is well known, and commercially available to varying degrees, and although it is not useful in this invention as the polyolefin elastomer (because of its relatively high density), it is useful as the crystalline polyolefin component of the polymer blend.

Linear ethylene copolymers and at least one alpha olefin of 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms, are well known, commercially available and useful in this invention. As is well known in the art, the density of a linear ethylene / alpha olefin copolymer is a function of both the length of the alpha olefin and the amount of such monomer in the copolymer in relation to the amount of ethylene, alpha olefin and the greater the amount of alpha olefin present, the lower the density of the copolymer. Linear Low Density Polyethylene (LLDPE) is typically an ethylene copolymer and an alpha olefin of 3 to 12 carbon atoms, or 4 to 8 carbon atoms (for example, 1-butene, 1-hexene, 1- octeno, etc.), which has sufficient alpha-olefin content to reduce the density of the copolymer to that of LDPE. When the polymer contains even more alpha olefin, the density will fall below about 0.91 g / cm3 and these copolymers are known as ultra-low density polyethylene (ULDPE) or very low density polyethylene (VLDPE). The densities of such linear polymers will generally range from about 0.87 to 0.91 g / cm3.

Homogeneously branched polyethylenes which may be used in the practice of this invention also fall into two broad categories, homogeneously branched linear and substantially linear, homogeneously branched. Both are known. The former and their method of preparation are described in Elston US Patent 3,645,992 and the latter and their method of preparation are fully described in US 5,272,236, US 5,278,272 and US 5,380,810, all of which are herein. incorporated by reference. Examples of the former are Mitsui's Tafmer® polymer and Exxon's Exact® polymer, while an example of the latter are polymers made by Dow Chemical Company's Insite®, Process and Catalyst Technology.

As used herein, "substantially linear" means that the bulk polymer is replaced, on average, with about 0.1 long chain branch / 1,000 total carbons (including both main chain and branch carbons) to about 3 long chain branches / 1,000 total carbons, preferably from about 0.01 long chain branch / 1,000 total carbons to about 1 long chain branch / 1,000 total carbons, more preferably about from 0.05 long chain branch / 1,000 carbon atoms to about 1 long chain branch / 1,000 total carbons, and especially from about 0.3 long chain branch / 1,000 total carbons to about 1 long chain branch /1,000 total carbs.

"Long chain branching" or "Long chain branching" (LCB) means a chain length of at least (1) carbon less than the number of carbons in the comonomer, as opposed to "short chain branching" or "short chain branching" (SCB), which means a chain length of two carbons (2) less than the number of carbons in the comonomer. For example, a substantially linear ethylene / 1-octene polymer has long chain branched chains of at least seven (7) carbons in length, but it also has short chain branches of only six (6) carbons in length, whereas a substantially linear ethylene / 1-hexene polymer has long chain branches of at least five (5) carbons in length, but short chain branches of only four (4) carbons in length. LCB can be distinguished from SCB by the use of 13C nuclear magnetic resonance spectroscopy and to a certain extent, for example for ethylene homopolymers, it can be quantified using the Randall method (See. Macromol. Chem. Phys., C29 ( 2 & 3), pp. 285-297). However, as a matter of practice, current 13 C NMR spectroscopy cannot determine the length of an excess long chain branch of about six (6) and as such, this analytical technique cannot distinguish between a branch and a long branch. branch of seven (7) and one of seventy (70). The LCB may be about as long as the same length as the polymer backbone.

[Ο Ο 3 Ο] US Patent 4,500,648 teaches that the LCB frequency can be represented by the equation LCB = b / Mw where b is the weight average number of LCB per molecule and Mw is the weight average molecular weight. Molecular weight averages and LCB characteristics are determined by gel permeation chromatography (GPC) and intrinsic viscosity methods.

One measure of the SCB of an ethylene copolymer is its SCBDI (Short Chain Branch Distribution Index), also known as CDBI (Composition Distribution Branch Index), which is defined as the weight percentage of molecules. of polymer having an as-number content within 50% of the average total molar comonomer content. The SCBDI or CDBI of a polymer is readily calculated from data obtained from techniques known in the art, such as temperature-elution fractionation (TRFE) as described, for example, by Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), or as described in US Patent 4,798,081, which is incorporated herein by reference. The SCBDI or CDBI for the substantially linear ethylene polymers useful in the present invention is typically greater than about 30%, according to another embodiment greater than about 80%, and according to yet another embodiment greater than about 90%. .

"Polymer backbone" or just "backbone" means a discrete molecule, and "bulk polymer" or just "polymer" means the product that results from a polymerization process for substantially linear polymers, such a product may include both major chains of polymers having LCB, and main chains of polymers without LCB. Thus, a "bulk polymer" includes all major chains formed during polymerization. For substantially linear polymers, not all major chains have LCB, but a sufficient number have, so that the average LCB content of the mass polymer positively affects melt rheology (ie melt fracture properties).

These unique polymers, known as "substantially linear ethylene polymers", are prepared by the use of tensile geometry catalysts and are characterized by narrow molecular weight distribution and if an interpolymer, by narrow comonomer distribution. As used herein, "interpolymer" means a polymer of two or more comonomers, for example a copolymer, terpolymer, etc., or in other words, a polymer made by ethylene polymerization with at least one other comonomer. Other basic features of such substantially linear ethylene polymers include a low residue content (i.e. low concentrations of the substantially linear ethylene polymer of the catalyst used to prepare the polymer, unreacted comonomers, and low molecular weight oligomers made during polymerization). ), and a controlled molecular architecture that provides good processability although the weight distribution is narrow relative to conventional olefin polymers.

The melt flow rate, measured as I10 / I2 (ASTM D-1238 condition 190/10 for I10 and condition 190 / 2.6 for I2) of these substantially linear ethylene polymers is greater than or equal to 5.63, and is preferably from 6.5 to 15, more preferably from 7 to 10. The molecular weight distribution (Mw / Mn) as measured by gel permeation chromatography (GPC) is defined by the equation: MW / Mn is less than or equal to (I10 / I2) -4.63, and is between about 1.5 and about 2.5. For substantially linear ethylene polymers, the I10 / I2 ratio indicates the degree of long chain branching, that is, the higher the I10 / I2 ratio, the longer the long chain branching.

The unique characteristic of such homogeneously branched substantially linear ethylene polymers is a highly unexpected flow property where the polymer's I10 / I2 value is essentially independent of the polymer's polydispersity index (ie Mw / Mn). . This is in contrast to conventional homogeneously linear branched polyethylene resins (e.g. those described by Elston in US Patent 3,645,992) and conventional heterogeneously branched branched polyethylene resins (e.g. those prepared with a free radical generator , such as linear low density polyethylene) having rheological properties in order to increase the value of I10 / I2, then the polydispersity index should also be increased.

Substantially linear olefin polymers have a critical shear rate at the start of surface melt fracture of at least 50% greater than the critical shear rate at the start of surface melt fracture of a linear olefin polymer having about of the same I2, Mw / Mn and density. "About the same" means that the values are within about ten (10) percent of each other.

The preferred melt flow rate, or simply melt index, measured as I2 (ASTM D-1238, condition 190 / 2.16 (formerly condition E)) is 0.05 g / 10 min at 200 g / 10 min, more preferably from 0.5 to 20 g / 10 min. For example, in the case of EPDM, a melt index range of 0.05 to 200 g / 10 min corresponds to approximately a Mooney viscosity (ML (1 + 4), 121 ° C) of <1 to 70. According to With another embodiment of the present invention, the substantially linear ethylene polymers used are homogeneously branched and have no measurable high density fraction, i.e. curing chain branching distribution as measured by Temperature Gradient Elution Fractionation ( which is described in US Patent 5,089,321) or otherwise, these polymers do not contain any polymeric moiety having a degree of branch less than or equal to 2 methyl / 1,000 carbons. These substantially linear ethylene polymers also have a simple differential scanning calorimetry (DSC) melting peak between -30 ° C and 150 ° C at a scanning rate of 10 ° C / min using a second heat.

An apparent shear stress versus apparent shear rate graph is used to identify melt fracture phenomena. According to Rama-murthy in the Journal of Rheology, 30 (2), 337-357 (1986), above a certain critical flow rate, observed extrudate irregularities can be broadly classified into two major types: superficial melt fracture and coarse cast.

Surface melt fracture occurs under apparently constant flux conditions and varies in detail from loss of specular gloss to the most severe form of "shark skin". In this invention, the onset of surface melt fracture is characterized at the beginning of the extruded gloss loss as the surface roughness of the extrudate can only be detected by a magnification of 40 times or more. The critical shear rate at the start of surface melt fracture for the substantially linear ethylene polymers of this invention is at least about 50% higher than the critical shear rate at the start of surface melt fracture of a linear ethylene polymer having about the same I2, Mw / Mn and density. Coarse cast fracture occurs under non-constant flow conditions and varies in detail from regular distortions (alternating from rough and smooth, helical, etc.) to random.

The polyolefin elastomer component of such mixtures, which may be used, includes terpolymers, for example ethylene / propylene / diene (EPDM) monomers, tetramers, and the like. The diene monomer component of these elastomers includes both conjugated and unconjugated dienes. Examples of unconjugated dienes include aliphatic dienes such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,6-heptadiene, 6-methyl-1,5- heptadiene, 1,7-octadiene, 7-methyl-1,6-octadiene, 1,13-tetradecadiene, 1,19-eicosadiene, and the like; cyclic dienes such as 1,4-cyclohexadiene, bicyclo [2.2.1] hept-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, bicyclo [2.2. 2] oct-2,5-diene, 4-vinicycloex-1-ene, bicyclo [2.2.2] oct-2,6-diene, 1,7.7-trimethylbicyclo [2.2.1] hept-2,5-diene, dicyclopentadene, methyl tetrahydroindene, 5-allylbicyclo [2.2.1] hept-2-ene, 1,5-cyclooctadiene, and the like; aromatic dienes such as 1,4-diallylbenzene, 4-allyl-1H-indene; and trienes such as 2,3-diisopropenylidiene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, and the like. . According to another embodiment, unconjugated diene is 5-ethylidene-2-norbornene.

Examples of conjugated dienes include butadiene, isoprene, 2,3-dimethylbutadiene-1,3,2,2-dimethylbutadiene-1,3, 1,4-dimethylbutadiene-1,3,1-ethylbutadiene-1,3, 2-phenylbutadiene-1,3, hexadiene-1,3,4-methylpentadiene-1,3,3-pentadiene (CH 3 CH = CH-CH = CH 2; commonly called piperylene), 3-methyl-1,3-pentadiene pentadiene, 2,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, and the like. In another embodiment, the conjugated diene is a 1,3-pentadiene.

Examples of terpolymers include ethylene / propylene / 5-ethylidene-2-norbornene, ethylene / 1-octene / 5-ethylidene-2-norbornene, ethylene / propylene / 1,3-pentadiene, and ethylene / 1- octene / 1,3-pentadiene. Examples of tetrapolymers include ethylene / propylene / mixed dienes, for example ethylene / propylene / 5-ethylidene-2-norbornene / piperylene.

The crystalline polyolefin polymer component of the mixture has a crystallinity of at least about 40%, preferably at least about 50% and more preferably at least about 60%, preferably in combination with a melting point greater than 10%. about 100 ° C, more preferably greater than about 120 ° C. The crystallinity percentage is determined by dividing the melt heat as determined by DSC of a polymer sample by the total melt heat for that polymer sample. Preferred crystalline polyolefins include high density polyethylene (as described above), and polypropylene. The total heat of fusion for high density (i.e. 100% crystalline) polyethylene homopolymer is 292 joules / q (J / q), and the total heat of fusion for 100% crystalline polypropylene is 209 J / q.

If the crystalline polyolefin component of this invention is polypropylene, then it may be either a homopolymer or one or more propylene copolymers and up to 20 molar percent ethylene or at least one alpha olefin having up to about 12 carbon atoms. . If a copolymer, then it may be random, block or grafted, and may be either isotactic or syndiotactic. The polypropylene component of this invention has a typical melt flow rate (as determined by ASTM D-1238, Procedure Conditions A (for I2) and N (for I10) at a temperature of 230 ° C) from about 0.1 to about 100 q / 10 min, and preferably between about 0.8 to about 30 g / 10 min.

The blend composition may vary widely, but typically the weight ratio of polyolefin elastomer: crystalline polymer is at least about 70:30. According to another embodiment, the weight ratio of polyolefin elastomer: crystalline polymer is at least about 80:20. In yet another embodiment, the weight ratio of polyolefin elastomer: crystalline polymer is at least about 85:15. The weight ratio of polyolefin elastomer: crystalline polymer typically does not exceed about 99: 1.

Suitable silanes for the present invention include silanes of the general formula [Y [-G (-SiXuZ * vZcw) s] r] n (Formula 1) wherein each occurrence of G is independently selected from a group of groups comprising a a free-living group derived by substitution of one or more hydrogen atoms of an alkyl, alkenyl, aryl or aralkyl group, or a molecular component which may be obtained by removal of one or more hydrogen atoms from a heterocarbone, with G containing from about 1 to about 30 carbon atoms; each occurrence of X is independently selected from the group consisting of -Cl, -Br, R10-, R1C (= 0) 0-, R1R2C = NO—, R1R2NO- or R1R2N-, -R1, - (OSiRiR2) t (OSiR1R2R3) ), and - O (R10CR1; L) fOH, wherein each occurrence of R1, R2, R3, R10 and R11 is independently R; each occurrence of Zb is independently (—O—) o, 5, and [-0 (R10CR11) fO-] o, 5, where each occurrence of R10 and R11 is independently R; each occurrence of Zc is independently given by -0 (R10CR1; L) fO-, where each occurrence of R10 and R11 is independently R; each occurrence of R is independently selected from the group of groups comprising hydrogen; linear, cyclic or branched alkyl groups and may contain unsaturated alkenyl groups, aryl groups and aralkyl groups; or molecular components obtained from the removal of one or more hydrogen atoms from a heterocarbon; each occurrence of R containing from 1 to about 20 carbon atoms; each occurrence of subscript f is an integer from 1 to about 15, each occurrence of n is an integer from 1 to about 100, with the proviso that when n is greater than 1, v is greater than 0 and all valences for Zb have a silicon atom attached thereto, each occurrence of subscript u is an integer from 0 to about 3, each occurrence of subscript v is an integer from 0 to about 3, each occurrence of subscript w is an integer from 0 to about 1, with the proviso that u + v + 2w = 3, each occurrence of subscript r is an integer from 1 to about 6, each occurrence of subscript t is an integer from 0 to about 50, and each occurrence of the subscript s is an integer from 1 to about 6; each occurrence of Y is an organofunctional group of valence r; and at least one cyclic and bridged organofunctional dialkoxy silane comprising the cyclic and bridged organofunctional dialkoxy silane composition containing at least one occurrence of Zb or Zc.

Group Y includes univalent organofunctional groups (r = 1), divalent organofunctional groups (r = 2), trivalent organofunctional groups (r = 3), tetravalent organofunctional groups (r = 4) as well as organofunctional groups of higher valence, were referred to as polyvalent organofunctional groups. The term free-living organofunctional group is to be understood herein to include univalent, divalent, trivalent and tetravalent organofunctional groups. According to another embodiment of the present invention, Y in the general formula 1 described above is CH 2 = CH-, CHR = CH-, or CR 2 = CR-. The present invention will be described more specifically with reference to exemplary embodiments thereof. However, it should be noted that the present invention is not limited to the following exemplary embodiments only.

Another embodiment of the present invention herein includes organofunctional groups such as mercapto and acyloxy groups such as acryloxy, methacryloxy and acetoxy. Another embodiment of the present invention includes herein univalent epoxies such as glycidoxy, -O-CH 2 -C 2 H 3 O. epoxycyclohexylethyl, -CH 2 -CH 2 -C 6 H 9 O; epoxycyclohexyl, -C 6 H 90; epoxy, -CR 6 (-O-) CR 4 R 5. Another embodiment of the present invention herein includes univalent organofunctional groups such as hydroxy, carbamate, -NR 4 C (= O) R 5; urethane, -OC (= O) NR 4 R 5; thiocarbamate, -NR 4 C (= 0) SR 5; thiourethane, -SC (= O) NR 4 R 5; thionocarbmate, -NR 4 C (= S) OR 5; thionourethane, -OC (= S) NR 4 R 5; dithiocarbamate, -NR 4 C (= S) SR 5; and dithiourethane, -SC (= S) NR 4 R 5. Another embodiment of the present invention herein includes univalent organofunctional groups such as maleimide; maleate and substituted maleate; fumarate and substituted fumarate; nitrile, CN; citraconimide. Another embodiment of the present invention herein includes univalent organofunctional groups such as cyanate, -OCN; isocyanate, -N = C = 0; thiocyanate, -SCN; isothio cyanate, -N = C = S; and ether, -OR4. Another embodiment of the present invention herein includes univalent organofunctional groups such as fluorine, -F, chlorine, -Cl; bromine, -Br; iodine, -I; and thioether, -SR4. Another embodiment of the present invention herein includes univalent organofunctional groups such as disulfide, -S-SR4; trisulfide, -S-S-SR4; tetrasulfide, -S-S-S-SR4; pentasulfide, -S-S-S-S-SR4; hexasulfide, -S-S-S-S-S-SR4; and polysulfide, -SxR4. Another embodiment of the present invention herein includes organofunctional groups such as xanthate, -SC (= S) OR 4; trithiocarbonate, -SC (= S) SR4; urea, -NR 4 C (= O) NR 5 R 6; thionoureid (also better known as thioureid), -NR 4 C (= S) NR 5 R 6; amide, R 4 C (= 0) NR 5 - and -C (= 0) NR 4 R 5 -; thionoamide (also known as thioamide), R4C (= S) NR4-; univalent melamine; and univalent cyanurate. Another embodiment of the present invention herein includes univalent organofunctional groups, such as primary amino, -NH2; secondary amino, -NHR4; and aminotertiary, -NR 4 R 5; univalent diamino, -NR4-L1-NR5R6; univalent triamino, -NR4-L1 (-NR5R6) 2 and -NR4-L1-NR5-L2-NR6R7; and univalent tetraamino, -NR4-L1 (-NR5R6) 3, -NR4-L1-NR5-L2-NR6-L3-NR7R8, and -NR4-L1-N (-L2NR5R6) 2} where each occurrence of L1, L2 and L3 is selected from the group of structures given above for G; each occurrence of R4, R5, R6, R7 and R8 is independently given by one of the structures given above; and each occurrence of the subscript, x, is independently given by x equal to 1 to 10.

Another embodiment of the present invention includes divalent organofunctional groups such as epoxy, - (-) C (-0-) CR4 R5 and -CR5 (-0-) CR4 -. Another embodiment of the present invention includes organofunctional groups such as carbamate, - (-) NC (= O) R 5; urethane, -0 ° C (= O) NR 4 -; thiocarbamate, - (-) NC (= 0) SR5; thiourethane, -SC (= O) NR 4 -; thionocarbmate, - (-) NC (= S) OR5; thionourethane, -OC (= S) NR 4 -; diothiocarbamate, - (-) NC (= S) SR5; dithiourethane, -SC (= S) NR 4 -; and ether, -O-. Another embodiment of the present invention herein includes divalent organofunctional groups such as maleate and substituted maleate; fumarate and substituted fumarate. Another embodiment of the present invention includes thioether, -S-; disulfide, -S-S-; trisulfide, -S-S-S-; tetrasulfide, -S-S-S-S-; pen-tassulfide, -S-S-S-S-S-; hexasulfide, -S-S-S-S-S-S-; and polysulphide, -Sx. Another embodiment of the present invention herein includes organofunctional groups such as xanthate, -SC (= S) O-; trithiocarbonate, -SC (= S) S-; dithiocarbonate, -SC (= O) S-; ureido, - (-) NC (= O) NR 4 R 5 and -NR 4 C (= S) NR 5 -; thionoureido, also better known as thioureido, - (-) NC (= S) NR4R5 and -NR4C (= S) NR5-; amide, R 4c (= 0) N (-) - and -C (= 0) NR 4 -; thionoamide, also better known as thioamide, R4C (= S) N (-) -; divalent melamine; divalent cyanurate. Another embodiment of the present herein includes divalent organofunctional groups, such as secondary amino, -NH-; tertiary amino, -NR 4 -; divalent diamino, - (-) N-L1-NR4R5 and -NR4-L1-NR5-; divalent triamino, (-) (NR4) 2-L1-NR5R6, - (-) N-L1-NR5-L2-NR6R7, -NR4-L1-N (-) -L2-NR5R6, and -NR4-L1-NR5 -L2-NR6-; and a divalent tetraamino, - (-) N-L1- (NR5R6) 3, (-NR4) 2-L1- (NR5R6) 2, - (-) N-L1-NR4-L2-NR5-L3-NR6R7, - NR4-L1-N (-) -L2-NR5-L3-NR6R7, -NR4-L1-NR5-L2-N (-) -L3-NR6R7, -NR4-L1-NR5-L2-NR6-L3-NR7, - (-) N-L1-N (-L2NR5R6) 2, and (-NR4L1-) 2N-L2r5r6. wherein each occurrence of L1, L2, and L3 is independently selected from the set of structures given above for G; each occurrence of R4, R5, R6, and R7 is independently given by one of the structures listed above for R; and each occurrence of the subscript, x, is independently given by x equal to 1 to 10.

Another embodiment of the present invention includes trivalent organofunctional groups such as epoxy, - (-) C (-0-) CR4 -. Another embodiment of the present invention herein includes trivalent organofunctional groups such as carbamate, - (-) NC (= 0) 0-; thiocarbamate, - (-) NC (= 0) S-; thionocarbamate, - (-) NC (= S) 0-; and dithiocarbamate, - (-) NC (= S) S-, urea, - (-) NC (= 0) NR4-; thionoureido, also better known as thioureido, - (-) NC (= S) NR4-; amide, -C (= O) N (-) -; thionoamide, also better known as thioamide, -C (= S) N (-) -; trivalent melamine; and trivalent cyanurate. Another embodiment of the present invention herein includes trivalent organofunctional groups such as tertiary amino, -N (-) -; trivalent diamino, - (-) - N-L1-NR4-; trivalent triamino, (-NR4) 3-L1, (-NR4) 2- L1-NR5-, - (-) N-L1-N (-) -L2-NR3R4, -NR4-L1-N (-) -L2 -NR5-, and - (-) N-L1-NR4-L2-NR5-; and trivalent tetraamino, - (-) N-L1-N (-) - L2-NR5-L3-NR3R4, -NR4-L1-N- (-) -L3-NR3R4, - (-) N-L1-NR5- L2-N (-) -L3-NR3R4, —NR4 — L1 — N (-) —L2 — NR3 — L3 — NR4, - (-) N-L1-N (-L2NR3R4) (-L2NR5-), and ( -NR4L1-) 3N; wherein each occurrence of L1, L2, and L3 is independently selected from the set of structures given above for G; and each occurrence of R4, R5, and R6 is independently given by one of the structures listed above for R.

Another embodiment of the present herein includes tetravalent organofunctional group such as epoxy, - (-) C (- O) C (-). Another embodiment of the present invention herein includes tetravalent organofunctional groups such as ureido, - (-) NC (= 0) Nthioureido (also better known as thioureido), - (-) NC (= S) tetravalent melamino. Another embodiment of the present invention herein includes tetravalent organofunctional groups such as tetravalent diamino, (-) N-L1-N (-) -; tetravalent triamino, (-NR4) 4-L1, (-NR4) 2-L1-N (-) -, - (-) N-L1-N (-) -L2-NR3-, and - (-) N- L1-NR4-L2 - (-) -; and tetravalent tetraamino, - (-) N-L1-N (-) -L2-N (-) -L3-NR4R3, -NR4-L1-N (-) - L2-N (-) -L3-NR3 -, - (-) N-L1-NR4-L2-NR3-L3-N (-) -, and - (-) Ν-ΐΛ-Ν- (-L2NR3-) 2; wherein each occurrence of L1, L2 and L3 is independently selected from the group of structures given above for G; and each occurrence of R4 and R5 is independently given by one of the structures listed above for R.

Another embodiment of the present invention herein includes polyvalent organofunctional groups such as, but not limited to, polyvalent hydrocarbon groups; pentavalent melamine, (-NR 3) (-N-) 2 C 3 N 3; hexavalent melamine, (-N-) 3 C 3 N 3; pentavalent triamino, - (-) N-L1-N (-) - L2-N (-) -; pentavalent te-traamino, - (-) N-L1-N (-) - L2-N (-) - L3-NR3-, - (-) N-L1 — NR3 — L2 — N (-) —L3 — N (-) -, and [- (-) -N-L1-] 2N-L2NR3-; and hexavalent tetraamino, - (-) N-L1-N (-) - L2-N (-) - L3-N (-) - and - (-) N-L1-] 3N; wherein each occurrence of L1, L2 and L3 is independently selected from the set of structures given above for G; and each occurrence of R4 is independently given by one of the structures listed above for R.

As used herein, diol hydrocarbon and difunctional alcohol refer to any structure given by Formula 2: wherein f, R 10, and R 11 are as defined above. Such structures represent hydrocarbons or heterocarbons, in which two hydrogen atoms are substituted with OH according to the structures shown in Formula 2. As used herein, dialkoxy and difunctional alkoxy refer to any diol hydrocarbon, as defined herein, wherein Hydrogen atoms of the two OH groups have been removed to give a divalent radical, and whose structure is given by Formula 3: wherein F, R10, and R11 are as defined above. As used herein, cyclic dialoxy refers to a silane or group in which cyclization is around silicon, by two oxygen atoms, each bonded to a common divalent hydrocarbon or heterocarbon group, as commonly found in diols. . Cyclic dialkoxy groups are represented herein by Zc. As used herein, bridged dialoxy refers to a silane or group in which two different silicon atoms are each bonded to a divalent hydrocarbon or heterocarbon group as defined herein, as commonly found in diols. Bridged dialkoxy groups are represented herein by Zb. As used herein, cyclic or bridged refers to a cyclic-only bridging silane group, without bridging; bridged only, no cyclic; and any combination of both cyclic and bridging. Thus, a cyclic or bridged silane can mean, for example, a silane with a silicon atom bonded to a cyclic dialoxy group, a silane with a silicon atom bonded to a cyclic dialoxy group and bonded to only one group (s) bridged dialoxy, a silicon with silicon bonded to both of one end of the dialoxy group and both ends of a cyclic dialoxy group, a silane with an unalloyed silicon atom, ally, to a dialoxy group (provided at least another silicon atom in the same molecule is bonded to at least one cyclic or bridged dialoxy group, etc. As used herein, hydrocarbon based diols refer to diols, which contain two OH groups in a hydrocarbon or heterocarbon structure. The term "hydrocarbon-based diol" refers to the fact that the main chain between the two oxygen atoms consists entirely of carbon atoms, carbon-carbon bonds between the carbon atoms, and two carbon-oxygen bonds. involving the alkoxy ends. The heterocarbons in the structure occur pending to the main carbon chain.

The structures given by Formula 2 will be referred to herein as the appropriate diol, in a few specific cases glycol is the most commonly used term prefixed by the particular hydrocarbon or heterocarbon group associated with the two OH groups. Examples include neopentylcycl, 1,3-butanediol, and 2-methyl-2,4-pentanediol.

Groups whose structures are given by Formula 3 will be referred to herein as the appropriate dialoxy, prefixed by the particular hydrocarbon or heterocarbon group associated with the two OH groups. Thus, for example, the diols, neopentylglycol, 1,3-butanediol, and 2-methyl-2,4-pentanediol correspond here to the dialkoxy, neopentyl glycoxy, 1,3-butanedialoxy groups, and 2-methyl-2,4-pentanedialoxy groups respectively.

The cyclic or bridged organofunctional dialkoxy silanes used herein, where silane is derived from a diol commonly referred to as a glycol, are correspondingly glycoxysilane. Also the cyclic and bridged organofunctional dialkoxy silanes used herein where silane is derived from a diol commonly referred to as a diol are correspondingly referred to as dialkoxysilane.

As used herein, the (-0-) o, 5 and [O (R10CR1; L) fO-] 0.5 structures refer to one half of a siloxane group, -Si-O-Si, and one half of a bridged dialoxy group, respectively. These structures are used in conjunction with a silicon atom and they are considered herein to mean one half of an oxygen atom, that is, the half attached to the particular silicon atom, or one half of a dialoxy group, that is, the half attached to the particular silicon atom, respectively. It is understood that the other half of the oxygen atom or alkoxy group and its bond to silicon occur somewhere else in the total molecular structure being described. Thus, the (-0-) o, 5 siloxane groups and the [-0 (R10CR1; L) fO-] 0.5 dialkoxy groups mediate the chemical bonds that hold the two silicon atoms apart together if these two silicon atoms occur intermolecularly or intramolecularly. In the case of [0 (R10CR1; L) fO-] 0.5, if the hydrocarbon group (R10CR1: L) f is asymmetric, either end of [-0 (R10CR1: L) fO-] 0.5 can be bonded to either of two silicon atoms to complete the structures given in Formula 1.

As used herein, alkyl includes linear, branched and cyclic alkyl groups; Alkenyl includes any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the substitution point may be at either a carbon-carbon double bond or elsewhere in the group. Also, alkynyl includes any straight, branched or cyclic alkynyl group containing one or more carbon-carbon triple bonds and optionally also one or more carbon-carbon double bonds, where the substitution point may be in a triple carbon-carbon bond. carbon, a carbon-carbon double bond, or elsewhere in the group. Specific examples of alkyls include methyl, ethyl, propyl, isobutyl. Specific examples of alkenyls include vinyl, propenyl, allyl, metalyl, ethylidenyl norbornane, ethylidene norbornyl, ethylidenyl norbornene and ethylidene norbornenyl. Specific examples of alkynyls include acetylenyl, propargyl and methylketylenyl.

As used herein, aryl includes any aromatic hydrocarbon from which a hydrogen atom has been removed; aralkyl includes any of the alkyl groups mentioned above where one or more hydrogen atoms have been replaced by the same and / or different number of aryl substituents (as defined herein); and arenyl includes any of the above mentioned aryl groups in which one or more hydrogen atoms have been substituted by the same and / or different number of alkyl substituents (as defined herein). Specific examples of aryls include phenyl and naphthalenyl. Specific examples of aralkyls include benzyl and phenethyl. Specific examples of arenyls include tolyl and xylyl.

As used herein, cyclic alkyl, cyclic alkenyl and cyclic alkynyl also include higher bicyclic, tricyclic, and cyclic structures, as well as the aforementioned cyclic structures substituted later with alkyl, alkenyl and / or alkynyl groups. Representative examples include norbornyl, norbornenyl, ethylborboryl, ethylboronenyl, ethylcyclohexyl, ethylcyclohexyl, cyclohexylcyclohexyl and cyclodecatrienyl.

As used herein, the term hydrocarbon refers to any hydrocarbon structure in which the carbon-carbon bond of the main chain is interrupted by bonding to nitrogen and / or oxygen atoms; or wherein the carbon-carbon bond of the backbone is disrupted by bonding to nitrogen and / or oxygen containing groups of atoms, such as cyanurate (C3N3O3). Thus, heterocarbons include, but are not limited to, straight chain, cyclic and / or polycyclic aliphatic hydrocarbons, optionally containing ether functionality via oxygen atoms, each of which is attached to two separate carbon atoms, tertiary amine functionality via nitrogen atoms, each of which is attached to three separate carbon atoms, melamino groups and / or cyanurate groups; Hydrocarbons; and arenes derived by substituting the above mentioned aromatics with straight or branched chain alkyl, alkenyl, alkynyl, aryl and / or aralkyl groups.

Representative examples of G include - (CH 2) m -, where m is from 1 to 12; diethylene cyclohexane; 1,2,4-triethylene cyclohexane; diethylene benzene; phenylene; - (CH2) p-, where p is 1 to 20, which represent terminal straight chain alkyls still terminally substituted at the other end, such as -CH2, -CH2H2-, -CH2CH2CH2-, and -CH2CH2CH2CH2CH2CH2CH2-, and their analogues beta-substituted, such as -CH 2 (CH 2) q CH (CH 3) -, where q is zero to 17; -CH 2 CH 2 C (CH 3) 2 CH 2 -; the metalyl chloride derivative structure, -CH 2 CH (CH 3) CH 2 -; any of the divinylbenzene derivable structures, such as -CH 2 CH 2 (C 6 H 4) CH 2 H 2 - and -CH 2 CH 2 (C 6 H 4) CH (CH 3) -, where the C 6 H 4 structure signifies a disubstituted benzene ring; any of the dipropenylbenzene derivable structures, such as -CH 2 CH (CH 3) (C 6 H 4) CH (CH 3) CH 2 -, wherein the C 6 H 4 structure signifies a disubstituted benzene ring; any of the butadiene derivative structures, such as -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH (CH 3) -, and -CH 2 CH (CH 2 CH 3) -; any of the piperylene derivable structures, such as CH2CH2CH2CH (CH3) -, -CH2CH2CH (CH2CH3) -, and -CH2CH (CH2CH2CH3) -; any of the isoprene derivable structures, such as CH 2 CH (CH 3) CH 2 CH 2 -, -CH 2 CH (CH 3) CH (CH 3) -, - CH 2 C (CH 3) (CH 2 CH 3) -,. -CH 2 CH 2 CH (CH 3) CH 2 -, -CH 2 CH 2 C (CH 3) 2- and -CH 2 CH [CH (CH 3) 2] -; any of the isomers of -CH2CH2-norbornyl-, -CH2CH2-cyclohexyl-; any of the norbornene, cyclohexane, cyclopentane, tetrahydrodicyclopen-tadiene, or cyclododecene di-radicals obtainable by loss of two hydrogen atoms; limonene derivable structures, -CH 2 CH (4-methyl-1-C 6 H 9) CH 3, where structure C 6 H 9 means isomers of the trisubstituted cyclohexane ring requiring replacement at position 2; any of the trivnylcycloexane-derived monovinyl-containing structures, such as -CH 2 CH 2 (vinylCeHg) CH 2 CH 2 -and -CH 2 CH 2 (vinylCeHg) CH (CH 3) -, wherein the CôHg structure designates any isomer of the tri-substituted cyclohexane ring; any of the tri-substituted C = C-mircene derivatized monounsaturated structures such as CH2CH [CH2CH2CH = C (CH3) 2] CH2CH2-, -CH2CH [CH2CH2CH = C (CH3) 2] CH (CH3) -, -CH2C [ CH 2 CH 2 CH = C (CH 3) 2] (CH 2 CH 3) -, - CH 2 CH 2 CH [CH 2 CH 2 CH = C (CH 3) 2] CH 2 -, -CH 2 CH 2 (C-) (CH 3) [CH 2 CH 2 CH = C (CH 3) 2], and CH 2 CH [CH (CH 3) [CH 2 CH 2 CH = C (CH 3) 2]] -; and any of the mono-unsaturated mircene structures lacking C = C, such as -CH 2 CH (CH = CH 2) CH 2 CH 2 CH 2 C (CH 3) 2-, - CH 2 CH (CH = CH 2) CH 2 CH 2 CH (CH 3) 2] -, CH 2 C (= CH -CH 3) CH 2 CH 2 CH 2 C (CH 3) 2-, -CH 2 C (= CH-CH 3) CH 2 CH 2 CH [CH (CH 3) 2] -. -CH2CH2C (= CH2) CH2CH2CH2C (CH3) 2, -CH2CH2C (= CH2) CH2CH2CH [CH (CH3) 2] -, -CH2CH = C (CH3) 2CH2CH2CH2C (CH3) 2-, and -CH2CH = C (CH3) CH 2 CH 2 CH [CH (CH 3) 2].

Representative examples of the R groups are H, branched or straight chain alkyl of 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, octenyl, cyclohexyl, phenyl, benzyl, tolyl, allyl, methoxyethyl, ethoxyethyl dimethylaminoethyl, cyanoethyl and the like. In another embodiment, representative groups R10 and R11 are hydrogen, methyl, and ethyl, of which hydrogen and methyl are most preferred. In yet another embodiment, representative R 1 and R 2 groups may be hydrogen, methyl, ethyl or propyl. In yet another embodiment, representative examples of R 3, R 4, R 5, R 6, R 7 and R 8 may be H, C 1 to C 4 straight chain or branched chain alkyls such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl , pentyl, hexyl, heptyl, octyl and aryl such as phenyl, benzyl, etc.

Specific examples of X are methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, acetoxy, methoxyethoxy, and oxyto, as well as monovalent alkoxy groups derived from diols, known as "dangling diols", specifically, groups containing an alcohol and an alkoxy such as (-O-CH 2 CH-OH), ethylene glycol, propylene glycol, neopenyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3- butanediol, 2-methyl-2,4-pentanediol, 1,4-butanediol, cyclohexane dimethanol and pinacol. In another embodiment, specific examples of X are methoxy, acetoxy and ethoxy, as well as the monovalent alkoxy groups derived from diols, ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol 1,3-butanediol and 2-methyl-2,4-pentanediol.

Specific examples of Zb and Zc may be divalent alkoxy groups derived from diols, such as ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3- butanediol, 2-methyl-2,4-pentanediol, 1,4-butanediol, cyclohexane dimethanol and pinacol. In another embodiment, specific examples of Zb and Zc are divalent alkoxy groups derived from diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediool, 2-methyl-1,3-propanediol, 1, 3-Butanediol and 2-methyl-2,4-pentanediol are preferred. Divalent alkoxy groups derived from diols, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, and 2-methyl-2,4-petanediol. The bridging content (Zb) of the cyclic and bridged organofunctional silane compositions should be kept sufficiently low to prevent excessive average molecular weights and crosslinking which would lead to freezing.

Additional embodiments are wherein v and w in Formulas 1 may be such that the w / v ratio is between 1 and 9; X is RO- or RC (= 0) 0-; Zb and Zc may be derived from diols, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol and 2-methyl-2,4-pentanediol; R is a C1 to C4 alkyl or H; and G is a divalent straight chain alkyl of 2 to 18 carbon atoms. Other modalities include those where w / v is between 2 and 8; X is ethoxy or one or more of the pendant diols derived from diols, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol and 2-methyl-2,4-pentanediol; and G is a C2 -C12 straight chain alkyl derivative. Another embodiment is wherein v in Formula 1 is 0; X is RO- or RC (=) 0-; R is a C1 to C4 alkyl or H; and G is a bivalent straight chain alkyl of 2 to 18 carbon atoms.

Representative examples of the cyclic and bridged organofunctional dialkoxy silanes described in the present invention include 1,3-propanedialcoxyethoxyvinylsilane; 1,3-propanedialoxyoxymethoxyvinylsilane; 1,3-propanedialcoxyisopropoxyvinylsilane; 2-methyl-2,4-pentanedialkoxymethoxyvinylsilane; 2-methyl-2,4-pentanedialoxyoxyethoxyvinylsilane; 2-methyl-2,4-pentanedialkoxyispropoxyvinylsilane; 1,3-butanedialalkoxymethoxyvinylsilane; 1,3-butanedialoxyoxyethoxyvinylsilane; 1,3-butanedialcoxyisopropoxyvinylsilane; neopentyl dialkoxymethoxy vinylsilane; neopentyl dialkoxyethoxy vinylsilane; neopentyl dialkoxyisopropoxyvinylsilane; 2,3-dimethyl-2,3-butanedialoxyoxymethoxyvinylsilane; 2,3-dimethyl-2,3-butanedialcoxyethoxyvinylsilane; 2,3-dimethyl-2,3-butanedialcoxyisopropoxyvinylsilane; 2-methyl-1,3-propanedialkoxymethoxyvinylsilane; 2-methyl-1,3-propanedialoxyethoxyvinylsilane; 2-methyl-1,3-propanedialkoxyisopropoxyvinylsilane; 2- (2-methyl-2,4-pentanedialkoxyethoxysilyl) -1-propyl amino; 2- (2-methyl-2,4-pentanedialkoxyisopropoxysilyl) -1-propylmercaptan; 2- (2-methyl-2,4-pentanedialkoxymethylsilyl) -1-propyl chloride; 2- (2-methyl-2,4-pentanodialcoxyphenylsilyl) -1-propyl bromide; 3- (1,3-butanedialcoxyethoxysilyl) -1-propyl iodide; 3- (1,3-butanedialkoxyisopropoxy-silyl) -1-propyl chloride; N- [3- (1,3-propanedialkoxyethoxysilyl) -1-propyl] phenyl amino; N- [3- (1,3-propanedialkoxyisopropoxysilyl) -1-propyl] methylamino; 3- (1,2-propanedialcoxyethoxysilyl) -1-propyl glycidyl ether; and 3- (1,2-propanedialkoxy isopropoxy-lil) -1-propyl methacrylate, both derivatives of propylene glycol; 3- (1,2-ethanedialcoxyethoxysilyl) -1-propyl acrylate and 3- (1,2-ethanedialcoxyisopropoxysilyl) -1-propyl acetate, both derivatives of ethylene glycol; 3- (neopentyl glycoxyethoxysilyl) -1-propyl amine and ether 3- (neopentyl glycoxyisopropoxysilyl) -1-propyl glycidyl, both derivatives of neopentyl glycol; 3- (2,3-dimethyl-2,3-butanedialcoxy ethoxysilyl) -1-propyl acrylate and 3- (2,3-dimethyl-2,3-butanedialcoxyisopropoxysilyl) -1-propyl methacrylate, both derivatives of pinacol; 3- (2,2-diethyl-1,3-propanedialcoxyethoxysilyl) -1-propyl mercaptan; S- [3- (2,2-diethyl-1, propanedialoxy isopropoxy) -1-propyl] ethyl thioether; bis [3- (2-methyl-1,3-propanedialkoxy ethoxysilyl) -1-propyl] disulfide; bis [3- (2-methyl-1,3-propanedialoxy iso-propoxysilyl) -1-propyl] trisulfide; bis [3- (1,3-butanedialcoxymethylsilyl) -1-propyl] tetrasulfide; bis [3- (1,3-propanedialkoxymethylsilyl) -1-propyl thioether]; 3- (1,3-propanedialcoxyphenylsilyl) -1-propyl glycidyl; tris-Ν, Ν ', N "- [3- (1,2-propanedialcoxymethylsilyl) -1-propyl] melamine and tris-Ν, Ν', N" - [3- (1,2-propanedialcoxyphenylsilyl) -1- propyl] melamine, both propylene glycol derivatives; 3- (1,2-ethanedialcoxymethylsilyl) -1-propyl chloride and 3- (1,2-ethanedialcoxyphenylsilyl) -1-propyl bromide, both derivatives of ethylene glycol; 3- (neopentyl glycoxymethylsilyl) -1-propyl acetate and 3- (neopentyl glycoxyphenylsilyl) -1-propyl octanoate, both derivatives of neopentyl glycol; 3- (2,3-dimethyl-2,3-butanedialcoxymethylsilyl) -1-propyl amine and 3- (2,3-dimethyl-2,3-butanodialcoxyphenylsilyl) -1-propyl amine, both derivatives of pinacol; 3- (2,2-diethyl-1,3-propanedialoxymethylsilyl) -1-propyl acrylate; 3- (2,2-diethyl-1,3-propanedialkoxyphenyl silyl) -1-propyl methacrylate; 3- (2-methyl-1,3-propanedialcoxyethylsilyl) -1-propyl glycidyl ether; 3- (2-methyl-1,3-propanedialcoxyphenylsilyl) -1-propyl acetate; 2- (2-methyl-2,4-pentanedialcoxy ethoxysilyl) -1-ethyl acrylate; 2- (2-methyl-2,4-pentanedialcoxy methoxysilyl) -1-ethyl bromide; 2- (2-methyl-2,4-pentanedialoxymethylsilyl) -1-ethyl benzenesulfonate; 2-methyl-2,4-pentanedialcoxy ethoxysilylmethyl methacrylate; 2-methyl-2,4-pentanedialoxyoxypropylsilylmethyl bromide; neopentylglycoxypropoxysilylmethyl amine; propylene glycoloxymethylsilylmethyl mercaptan; neopentylglycoxyethylsilylmethyl glycidyl ether; 2- (neopentylglycoxyisopropoxy-silyl) -1-ethyl butyrate; 2- (neopentylglycoxymethylsilyl) -1-ethyl propionate; 2- (1,3-butanedialcoxymethylsilyl) -1-ethyl acrylate; 3- (1,3-butanedialkoxyisopropoxysilyl) -4-butyl methacrylate; 3- (1,3-butanedialcoxyethylsilyl) -1-propyl mercaptan; 3- (1,3-butanedialcoxymethylsilyl) -1-propyl methanesulfonate; 6- (2-methyl-2,4-pentanedialkoxyethoxysilyl) -1-hexyl amine; 1- (2-methyl-2,4-pentanedialkoxyethoxy-yl) -5-hexyl acrylate; 8- (2-methyl-2,4-pentanedialkoxyethoxy-yl) -1-octyl methacrylate; 10- (2-methyl-2,4-pentanedialcoxyethoxysilyl) -1-decyl glycidyl ether; 3- (2-methyl-2,4-pentane di-alkoxyethoxysilyl) -1-propyl trifluoromethanesulfonate; 3- (2-methyl-2,4-pentanedialkoxypropoxysilyl) -1-propyl amine; N- [3- (2-methyl-2,4-pentanedialcoxyisopropoxy-silyl) -1-propyl] ethylene diamine; tris-Ν, Ν ', N "- [3- (2-methyl-2,4-pentanedialoxy-xysilyl) -1-propyl] diethylene triamine; tetrakis-N, N', N", N "'- [3 - (2-methyl-2,4-pentane-dialkoxyisopropoxysilyl) -1-propyl] triethylene tetramine; bis (3- (2-methyl-2,4-pentanedialoxyethoxy silyl) -1-propyl) sulfide; 6- ( 1,3-butanedialcoxyethoxysilyl) -1-hexyl amine 1- (1,3-butanedialcoxyethoxysilyl) -5-hexyl glycidyl ether ether 8- (1,3-butanedialcoxyethoxysilyl) -1-octyl acrylate; (1,3-butanedialoxyoxyethoxysilyl) -1-decyl; and bis (3- (2-methyl-2,4-pentanedialoxyethoxy silyl) -1-propyl thioether).

In another embodiment, the organofunctional cyclic dialkoxy silanes are analogues of cyclic dial and bridged to 3-chloro-1-propyltriethoxysilane (3-triethoxysilyl-1-propyl chloride) used as a starting point for the manufacture of silane coupling agents such as polysulfide silanes, such as triethoxysilyl propyl tetrasulfide referred to herein as TESPT, triethoxysilypropyl disulfide referred to herein as TESPD. Cyclic and bridged dialkoxy haloalkyl silanes are new and excellent alternatives to 3-triethoxysilyl-1-propyl chloride for use where reduced VOC emissions are desired.

The organofunctional and cyclic dialkoxy silane compositions included herein may comprise single components or various mixtures of individual components of cyclic and bridged organofunctional dialcoxy silane, organofunctional silane components, which contain only monofunctional alkoxy groups, and, optionally, also including other species. Synthetic methods result in a distribution of various silanes, in which the mixtures of the starting components are employed for the purpose of generating mixtures of cyclic and bridged organofunctional dialkoxy silane products. In addition, it is understood that the partial hydrolysates and / or condensates of such cyclic and bridged organofunctional dialkoxy silanes, also referred to as cyclic and bridged organofunctional dialoxy and / or silanols, may be encompassed herein by silanes as a by-product. most of the methods of making cyclic and bridged organofunctional dialkoxy silanes. Also, partial and / or condensed hydrolysates may occur upon storage of cyclic and bridged organofunctional dialkoxy silanes, especially under humid conditions, or under conditions in which residual wastewater from their preparation is not completely removed after preparation. In addition, partial to substantial hydrolysis of cyclic and bridged organofunctional dialkoxy silanes can be deliberately effected by incorporating the appropriate stoichiometry or excess water into the preparation methods described herein for silanes. Also, the siloxane content of the cyclic and bridged organofunctional dialkoxy silanes can be deliberately prepared by incorporating the appropriate stoichiometry or excess water into the silane preparation methods described herein. The silane structures herein encompass hydrolysates, and siloxanes are described in the structures given in Formula 1, wherein the subscripts, v, of Zb = (- 0-) o, 5 and / or u, of X = OH may be nouns, meaning substantially greater than zero.

The cyclic organofunctional dialkoxy silane and bridging compositions, if liquid, may be loaded into a vehicle or a mixture of more than one vehicle, such as porous polymer, carbon black, or an inorganic filler. , such as silica, alumina, various clays, etc. When loading the composition into a vehicle it is in solid form for delivery to the polymer formulation. In another embodiment, the vehicle will be part of the charge, either intimately absorbed on or in, or chemically linked to the charge.

Silane compounds with heterocyclic silicon groups included herein may be prepared by transesterification of organofunctional alkoxy-substituted silanes and diols with or without catalyst, esterification of organofunctional silyl halides with diols, or by hydrosilylation of the compounds. a hydrosyl substituted alkenes containing a heterocyclic silicon group to generate cyclic or bridged silane compositions.

Transesterification of organofunctional alkoxy substituted silanes and diols may be conducted with or without catalyst. The catalyst may be an acid, a base or a transition metal catalyst. Suitable acid catalysts include hydrochloric acid, p-toluenesulfonic acid and the like. Typical base catalysts include sodium methoxide and sodium ethoxide. Suitable transition metal catalysts are tetraisopropyl titanate and dibutyltin dilaurate.

During esterification of organofunctional silica halides with diols, the diols are added to the silyl halide with removal of the formed hydrogen halide. Hydrogen halide may be removed by nitrogen sparging or reduced pressure. Any remaining halo groups may be removed by the addition of an alcohol such as methanol, ethanol, isopropanol and the like.

In another embodiment of the present invention, diol-derived organofunctional silane may be prepared by reacting a catalyzed mixture of organofunctional silane reagent and diol with simultaneous distillation. The reaction leads to the exchange of alcohol of one or more alkoxy groups selectively on the silicon atom of the organofunctional silane reagent with the diol. The reaction is triggered by the removal of the most volatile alcohol by-product by distillation. Suitable catalysts include acids such as p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, chlorosilanes, chloroacetic acids, phosphoric acid, mixtures thereof and so on; bases such as sodium ethoxide; and transition metal containing catalysts such as titanium alkoxides, titanium containing chelates, zirconium alkoxides, zirconium containing chelates and mixtures thereof.

In yet another embodiment of the present invention, diol-derived organofunctional silane may be prepared by catalyzing a mixture of organofunctional silane and diol in a first embodiment at a molar ratio of at least about 0, 5 mol diol per alkoxy silyl group to be transesterified, in a second embodiment, in a molar ratio of about 0.5 to about 1.5 for a trialkoxy silane; and in a third embodiment, from about 1.0 to about 1.5 for a trialkoxy silane. In each of the above embodiments, the reaction temperature may range from about 10 ° C to about 150 ° C and in another embodiment from about 30 ° C to 90 ° C while the pressure is maintained in the range of about from 13,3322 to about 266,644 absolute Pa (about 0.01 to about 2,000 mmHg absolute), and in another embodiment from about 133,322 to 10,665.76 absolute Pa (about 1 to about 80 mmHg absolute) . Excess diol can be used to increase the reaction rate.

In another embodiment, the diol-derived organofunctional silane may be prepared by slowly adding diol to the organofunctional silane in the presence of catalyst at the desired reaction temperature and under vacuum. If desired, a neutralization step may be used to neutralize any acid or base catalyst that may have been used thereby, thereby enhancing product storage.

Optionally, an inert solvent may be used in the process. The solvent may serve as a diluent, carrier, stabilizer, reflux aid or heating agent. Generally, any inert solvent, that is, one that does not enter the reaction or adversely affects the reaction, may be used. In one embodiment, solvents are those that are liquid under normal conditions and have a boiling point below about 150 ° C. Examples include aromatics, hydrocarbons, ethers, aprotic solvents and chlorinated hydrocarbon solvents such as toluene, xylene, hexane, butane, diethyl ether, dimethylformamide, dimethyl sulfoxide, carbon tetrachloride, methylene chloride and so on. .

In another embodiment of the present invention, diol-derived organofunctional silane may be prepared by continuously premixing the flow streams of the organofunctional silane reagent, diol and catalyst (when employed) at appropriate ratios and then introducing it. premixed reagents in the reactive distillation system, in one embodiment, a thin film device operating under the desired temperature and vacuum reaction conditions. Conducting the reaction on a thin film under vacuum accelerates the removal of the alcohol byproduct and improves the transesterification reaction rate. Vaporization and removal of the alcohol by-product from the film displaces the chemical equilibrium of the reaction in favor of the desired product formation and minimizes unwanted side reactions.

[0080] The above process embodiment comprises the steps of: a) reacting, in a thin film reactor, a thin film reaction medium, which comprises an organofunctional silane, for example a thiocarboxylate silane, diol and catalyst for providing diol-derived organofunctional silane and the alcohol by-product; b) spraying the alcohol by-product of the thin film to drive the reaction; c) recovering the diol-derived organofunctional silane reaction product; d) optionally recovering the alcohol by-product by condensation; and e) optionally neutralizing the diol-derived organofunctional silane product to improve its storage stability.

The molar ratio of diol to organofunctional silane reagent used in the continuous thin film process will depend on the number of alkoxy groups desired to be substituted with diol. In one embodiment of the thin film process, an equivalent steguiometric molar ratio of 1 is used, in which one diol replaces two alkoxy groups. In general, for practicing this embodiment, the molar ratio of diol to organofunctional silane can be varied in the range of about 95 to about 125% stoichiometric equivalence for each alkoxy silyl group to be transesterified. In a particular embodiment, the molar ratio of diol to organofunctional silane may be in the range of from about 100 to about 110% stoichiometric equivalence. In another embodiment, the molar ratio may be within the range of from about 100 to about 105% stoichiometric equivalence for the diol to organofunctional silane molar ratio. Those skilled in the art will recognize that excess diol could be used to increase reaction rates, but this does not ordinarily have a significant advantage when the reaction is being conducted on a thin film and only increases the expense.

[0082] The apparatus and method for forming the film is not critical and may be any of those known in the art. Typical known devices include falling film or clean film evaporators. The minimum film thickness and flow rates will depend on the minimum wetting rate for the film forming surface. Maximum film thickness and flow rates will depend on the flood point for the film and apparatus. The alcohol vaporization of the film is effected by heating the film, reducing the pressure on the film or by combining both. It is preferred that mild heating and reduced pressure be used to form the diol-derived organofunctional silane of this invention. Optimal temperatures and pressures (vacuum) to run the thin film process will depend on the specific organofunctional starting, diol and diol alkoxy groups used in the process. The present invention will be described more specifically by reference to exemplary embodiments thereof. However, it should be noted that the present invention is not limited to the following exemplary embodiment only.

According to an exemplary embodiment of the present invention, there is provided a process for preparing a silane composition comprising reacting at least one organofunctional silane with a diol in the presence or absence of catalyst to provide an organofunctional silane derived from. of diol.

In a first embodiment of the present invention, the silane compound is present in the range from about 0.1 to about 10% by weight, and all ranges between it, based on the total weight of the polymer, in a range. a second embodiment in the range from about 0.3 to about 3 wt%, in a third embodiment in the range from about 0.5 to about 2 wt%.

The term "silane modified polymer" as used herein means a polymer to be crosslinked, which is obtained by chemically introducing the silane represented by Formula 1 as described in its structure, for example employing a radical generator. free.

Free radical generators, which may be employed in the present invention, are those which decompose upon heating and generate free radicals. Free radical generators may be organic peroxides or peresters. The term organic peroxide means to include benzoyl peroxide, dichlorobenzoyl peroxide, dipropionyl peroxide, t-butyl peroxyisobutyrate or lauroyl peroxide; organic peroxides such as t-butyl peracetate, t-butyl peroxy-2-ethyl hexanoate, or t-butyl peroxy isobutyrate, t-butyl peroxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5- di (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexine-3, di-t-butyl peroxide, 2,5-di (peroxybenzoate) hexyl 3 or 1,3-bis (t-butyl-peroxyisopropyl) benzene; azo compounds such as azobiisobutyronitrile, azoisobutylvaleronitrile or dimethyl azodiisobutyrate; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexane peroxide or 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane; hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, para-menthane hydroperoxide or 2,5-dimethylhexane-2,5-dihydroperoxide; dialkyl peroxides such as di-t-butyl peroxide and peroxy esters such as t-butylperoxy acetate, t-butylperoxy benzoate, di-t-butyldiperoxy phthalate, 2,5-dimethyl-2,5-di (benzoyl) peroxy) hexane, t-butylperoxy maleate or t-butylperoxy isopropyl carbonate. In one embodiment, the free radical generator is dicumyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di (t-butiperoxy) hexane or molecular oxygen. The free radical generators described above may be used either alone or as a mixture of two or more. According to another embodiment, the free radical generator is an organic peroxide such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, alpha-bis (tert-butylperoxy) diidopropylbenzene or di-tertiary peroxide. butyl According to one embodiment of the present invention, the free radical generator is dicumyl peroxide. The criteria for choosing an appropriate free radical generator are known to those skilled in the art and are described in the above-mentioned US Patent 3,646,155, which is incorporated herein by reference and will not be repeated herein.

The amount of free radical scavenger may be varied within broad ranges, for example from about 0.01 wt.% To about 0.4 wt.%, And all ranges included thereon, based on total weight of the polymer. According to another embodiment, the amount of free radical scavenger is from about 0.02 to about 0.2% by weight. According to yet another embodiment, the amount of free radical scavenger is from about 0.02 to about 0.1% by weight.

If desired, a chain transfer agent may optionally be employed in the present invention to deactivate any portion of the free radical generator that remains unreacted when the silane modifying polymer is in the presence of the generator. of free radicals. Examples of suitable chain transfer agents are dodecyl mercaptan, t-butyl mercaptan, n-butyl mercaptan, octyl mercaptan and alpha methylstyrene. The chain transfer agent inhibits the crosslinking reaction of, for example, polyethylene and allows the binding reaction to the silane compound to proceed effectively.

According to one embodiment of the present invention, the chain transfer agent is a paraffin such as methane, ethane, propane, butane and pentane; alpha-olefins such as propylene, butene-1, and hexene-1; aldehydes such as aldehyde, acetaldehyde, and n-butylaldehyde; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons; and hydrochlorides.

Further, when such a chain transfer agent is used, it is present in the amount of from about 0.01 to about 0.5 part by weight per 100 parts by weight of the silane modified polymer. According to another embodiment, the chain transfer agent is from about 0.03 to about 0.1 part by weight per 100 parts by weight of the silane modified polymer.

Introduction of silane into the structure of the polymer to be crosslinked should ordinarily be obtained under substantially anhydrous conditions in order to prevent any significant amount of hydrolysis / premature condensation of silane fractions. Only after the selected silane is chemically introduced into the selected polymer (s) will the crosslinkable composition be exposed to a source of moisture that will result in hydrolysis / condensation whereby the polymer (s) will become crosslinked. While this step may be conducted in the absence of catalyst, hydrolysis / condensation catalyst may optionally be employed to accelerate crosslinking.

The optional hydrolysis / condensation catalyst may be an organic base, a carboxylic acid or an organometallic compound including organic and complex titanates or lead, cobalt, iron, nickel, zinc and tin carboxylate.

According to another embodiment of the present invention, the hydrolysis / condensation catalyst is an organometallic compound such as dibutyltin dilaurate, stannous acetate, stannous octanoate (stannous caprylate), lead naphthenate, zinc caprylate, 2-ethylhexanoate. iron, cobalt naphthenate; titanic acid esters and titanium chelate compounds (for example, tetrabutyl titanate, tetranonyl titanate, or bis (acetylacetonitrile) diisopropyl titanate); an organic base such as ethylamine, hexylamine, dibutylamine, piperidine or pyridine; an acid such as inorganic acids (e.g. hydrochloric acid and phosphoric acid) or a fatty acid (e.g. stearic acid, linoleic acid and octylic acid). These catalyst compounds can be used either alone or in mixtures. According to one embodiment of the present invention, higher carboxylic acid zinc salts may be used, such as aliphatic or alicyclic carboxylic acid zinc salts containing from 8 to 20 carbon atoms. According to yet another embodiment of the present invention, the catalyst is an alicyclic carboxylic acid containing from 8 to 17 carbon atoms. According to yet another embodiment, examples of such zinc salts include zinc stearate, zinc octanoate, zinc laurate, and zinc naphthenate. According to yet another embodiment of the present invention, the zinc salt is zinc stearate.

Zinc salts of higher carboxylic acids may be mixed with a small amount of another silane hydrolysis / condensation catalyst of the species exemplified above, for example, organotin compounds such as dibutyltin dilaurate, maleate dibutyltin or dibutyltin diacetate. The amount of other catalyst in the mixture should be minimized. For example, the other catalyst is limited to no more than 5% based on the total weight of the mixed catalyst.

According to another embodiment of the present invention, the catalyst is selected from the group consisting of dibutyltin dilaurate, dibutyltin diacetate, dibutyltin octanoate, dioctyltin maleate, dibutyltin oxide, dictyl tin bis (isooctyl maleate), dioctyl tin-bis (isooctyl thioglycolate) and titanium compounds such as titanium-2-ethylhexoxide. According to another embodiment of the present invention, the catalyst is dibutyltin dilaurate.

The hydrolysis / condensation catalyst, if used herein, will typically be present, in a first embodiment, in an amount from about 0.01 to about 1.0% by weight, in a second embodiment of 0.05. at about 0.5 wt%, in a third embodiment from 0.1 to about 0.2 wt%, based on the total weight of the polymer to be crosslinked.

Optionally, blowing agents may be incorporated into the present invention to produce polymeric foams. Blowing agents are blowing agents that decompose at a temperature of more than 140 ° C to generate gas. According to another embodiment, the blowing agents decompose between about 170 ° C and about 220 ° C to generate gas. According to another embodiment, the blowing agent is azodicarbonamide, dinitrosopentamethylenetetramine, p, p'-oxybis (benzenesulfonylhydrazide), N, N'-dimethyl-N, Ν'-dinitrosoterephthalamide and the like, or a physical blowing agent such as hydrocarbons (eg butane, penethane) and halogenated hydrocarbons (eg methyl chloride). The blowing agents mentioned above may be used individually or in any combination thereof. According to another embodiment, the blowing agent is azodi carbonamide. Azodicarbonamide is especially advantageous because of its good thermal stability and proper decomposition temperature.

The amount of blowing agent may be varied over a wide range according to, for example, the required degree of expansion of the final shaped, foamed article. Usually, the blowing agent is present in the amount of at least 0.1 part by weight per 100 parts by weight of the silane modified polymer. In another embodiment, the blowing agent is present in the amount of from about 1 to about 30 parts by weight per 100 parts by weight of the silane modified polymer. In yet another embodiment, the blowing agent is present in the amount of from about 10 to about 20 parts by weight per 100 parts by weight of the silane modified polymer.

When a thermo-decomposing blowing agent is employed, the free radical generator used to introduce silane into the structure of the polymer to be cross-linked advantageously has the same or similar decomposition temperature as that of the blowing agent, thus decomposing. simultaneously with the decomposition of the blowing agent. The free radical agent may be an organic peroxide having a decomposition temperature greater than about 140 ° C, for example, a decomposition temperature in the range of about 170 ° C to about 220 ° C.

Optionally, one or more conventional known additives may be included in the composition of the present invention including, for example, carbon black, talc, calcium carbonate, foaming agents, lubricants, antioxidants, compatibilizers, mineral fillers, flame retardant additives, ultraviolet decay inhibitor stabilizers, heavy metal decay inhibitor stabilizers, coloring agents, fillers, plasticizers, processing aids, pigments, thermostabilizers, compatibilizers, alumina trihydrate, zeolites, chalk, mica , silica, or silicates, and surge arresters.

According to another embodiment of the present invention, the coloring agent may be cadmium yellow, quinacridone red, cobalt blue, cadmium red, iron red oxide, titanium oxide, zinc oxide or carbon black. -smoke; nucleating agents may be talc, di-atomaceous earth, calcium carbonate, zinc stearate or aluminum stearate; lubricants may be paraffin or stearic acid; stabilizer may be 2-hydroxy-4-methoxybenzophenone or 2,6-di-tert-butylhydroxytoluene; fire retardants may be antimony oxide or chlorinated paraffin; fillers may be calcium oxide, magnesium oxide, sodium carbonate, potassium carbonate, strontium carbonate, barium sulphate, lithopone, magnesium carbonate, calcium carbonate, silica, kaolin, clay or talc; Foaming aids may be zinc oxide, zinc stearate or zinc octanoate, and spoilage inhibitors may be t-butyl p-cresol or dilauryl triopropionate in the amounts usually employed in the art.

According to another embodiment of the present invention, minerals may be used to improve flame retardancy or as an internal source of water for crosslinking, for example alumina trihydrate, zeolites or mineral fillers such as chalk, talc, mica, silica, silicates or carbon black.

According to another embodiment of the process of the present invention, cross-linking of the polymer is effected by the process comprising: a) combining under substantially moisture-free conditions: (i) thermoplastic base polymer, (ii) solid carrier polymer (iii) hydrolysable silane which, upon hydrolysis of its hydrolysable sites, produces a reduced amount of volatile organic compound compared to that produced by hydrolysis of a silane having an equivalent number of hydrolysable sites, all of which are hydrolysable alkoxy groups, (iv) a free radical generator and optionally (v) catalyst for silane hydrolysis / condensation reactions (iii) when silane (iii) is exposed to moisture; b) heating the resulting combination of step (a) to a temperature above the crystalline melting point of polymer (i) to graft the silane (iii) into the base polymer (i); and c) exposing the resulting product from step (b) to moisture to effect hydrolysis / condensation of grafted silane (iii), thereby providing grafted base polymer (i).

According to another exemplary embodiment, step (a) in the above process may be performed by: (al) combining polymer (ii), silane (iii) and free radical generator (iv) to provide a pre -mixture, in which silane (iii) and free radical generator (iv) are physically incorporated into the carrier polymer (ii); and (a2) combining the premix resulting from step (al) with the base polymer (i), optionally with the catalyst (v). When conducting (al), silane (iii) and free radical generator (iv) may, if desired, be combined to form a mixture, the resulting mixture thereafter being combined with carrier polymer (ii) to form the mixture. premix.

In conducting step (a2), the base polymer (i) and catalyst (v) may if desired be combined to provide a mixture, the resulting mixture thereafter being combined with the resulting premix. step (al).

The carrier polymer (ii) may be present within in its admixture with base polymer (i), for example, in a first embodiment at a level of from about 0.01 to about 40% by weight, and in a second embodiment at a level of from about 0.1 to about 20% by weight.

The base polymer (i) is any thermoplastic polymer or combination of polymers described above where silane is introduced prior to crosslinking. Base polymer (i) is typically supplied in pellet or granular form.

Silane (iii) suitable for grafting on and crosslinking with the base polymer (i) according to the present invention includes silanes of general Formula 1 as described above.

The amount of silane (iii) employed will be that which provides the desired degree of crosslinking. The amount of silane (iii) based on the weight of the base polymer (i), for example polyethylene, is not strictly critical and may range from about 0.01 to about 10% by weight, and all ranges between This is silane based on the total weight of the base polymer. According to another embodiment, the silane compound ranges from about 0.05 to about% by weight based on the total weight of the base polymer. In yet another embodiment, the silane compound ranges from about 0.05 to about 0.02% by weight based on the total weight of the base polymer.

Suitable free radical generators for initiating silane grafting on the base polymer (i) include any of the free radical generators described above.

Suitable hydrolysis / condensation catalysts for crosslinking the base polymer include the catalysts described above.

The carrier polymer (ii) used in the present invention is solid and must be compatible with the base polymer (i). "Compatible" means that the carrier polymer will not readily react with silane (iii) and will be dispersible or soluble in the base polymer at the latter's melting temperature. Examples of suitable carrier polymers are non-hygroscopic, ie moisture absorption is comparatively low to minimize the possibility of premature hydrolysis and silane condensation. In any case, the carrier polymer should be substantially free of water. In general, the carrier polymers of the present invention are particulate in the form of powder, granules or pellets. According to another embodiment of the present invention, the particulates are in the form of pellets.

The carrier polymer (ii) should be able to physically incorporate a silane represented by Formula 1 as described above, while its particulate and sodium characteristics are still retained. The three classes of carrier polymer (ii) are porous, sponge-like polymers, swellable and encapsulated polymers.

Porous polymers are capable of incorporating silane into the pores. Porous, sponge-like carrier polymers suitable for absorbing silane may be prepared, for example, from various high and low density polyethylenes and polypropylenes. According to one embodiment, the carrier polymer may be ethylene vinyl acetate (EVA) copolymer, high density polyethylene, low density polyethylene or linear low density polyethylene. The pore volume of the porous polymer is large enough to hold a relatively large volume of silane. The pore volume is generally from about 10 to about 90% of the porous polymer. According to another embodiment of the present invention, the pore volume is from about 30 to about 90%. The pore cross section is generally in the range of from about 0.1 to about 5 pm and the cell size is generally from about 1 to about 30 pm. Such porous polymers may absorb about 0.5 to about three times their weight of silane. Porous polymers may be employed as carrier polymers in the form of powder, pellet or pellet. Filled porous polymers are commercially available and can be obtained from ENKA AG, Accu-rel Systems, Postfach, 8753 Obernberg, FRG, or prepared as taught in US Patent 4,247,598, which is incorporated herein by reference.

Swellable polymers are capable of incorporating silane when swollen by silane. The carrier polymer may also be selected from polymers which are readily swelled by silane and optionally by peroxide, hydrolysis / condensation catalyst, stabilizers and other additives, where these may be mixed with or dissolved in silane to form a liquid mixture. A suitable polymer for this purpose is EVA, especially EVA having a high vinyl acetate content ranging from about 18 to about 45% by weight. Such swellable carrier polymer may be used in granules, powders, gums, or other solid forms. According to another embodiment of the present invention, the carrier polymer should be selected such that the amount of silane it can absorb without becoming wet or sticky is a minimum of about 10% by weight.

In practice, it has been found that suitable non-tumescent pellets containing about 20% vinyltrimethoxysilane can be prepared from EVA made from 26% vinyl acetate monomer. Polyethylene is generally not suitable as a suitable carrier polymer because it does not readily and sufficiently absorb large amounts of silanes.

[00117] A third class of carrier polymer (ii) is an encapsulated. Silane is encapsulated, this is contained with a thermoplastic polymer capsule. Suitable polymers useful as encapsulated in the present invention are polyolefins. Suitable polyolefins may be either an alpha olefin homopolymer having from 2 to 6 carbon atoms or a two alpha olefin copolymer. For example, encapsulating silane in the carrier polymer (ii) would produce a suitable solid form of silane.

The amount of carrier polymer (ii) is usually selected to be the minimum amount to contain the desired amount of silane and optionally one or more other additives in an easy-to-handle, dry form.

Generally, the absorption of silane, alone or with other additives in liquid form, in the carrier polymer in the process of the present invention is conducted by drum mixing the carrier polymer, silane, and optionally the other additives together. Drum mixing, for example, can be conducted in a Conus mixer. If not all additives are liquid, then any solid components must first be dissolved in silane. Mixing is performed under a layer of nitrogen, carbon dioxide, or dry air in a closed system to keep the silane substantially free of water and to minimize evaporation of liquid ingredients. Optionally, during mixing, heat may be applied. The container in which mixing occurs must be non-reactive with silane and other additives. Absorption of silane and any other liquid additive in the carrier polymer is performed prior to feeding the silane into the mixer and formulator apparatus. Additives absorbed in the carrier polymer together with silane may be incorporated, for example, into about 0.5 to 50% by weight of the carrier polymer, in another embodiment of about 0.5 to 10% by weight, and in addition. another embodiment of about 1.0 to 2.5% by weight.

According to another embodiment of the present invention, the process temperature generally ranges from above the crystalline melting point of the base polymer, i.e. between 120 ° C and the polymer degradation temperature. According to another embodiment, the process temperature ranges from about 150 ° C to about 225 ° C. The actual processing temperature employed will normally be determined by consideration of the polymers being processed and the type of apparatus in which the process is performed.

The process of the present invention may be carried out by employing any suitable apparatus. According to one embodiment of the present invention, the process is carried out under conditions under which the base polymer and the silane-containing solid carrier polymer of the present invention are subjected to mechanical work such as kneading and formulation. The process is therefore performed on, for example, an extruder. The use of such an apparatus for producing a crosslinked polymer is explained in detail in US Patent 5,112,919, the contents of which are incorporated herein by reference. Former common extruders are single screw or twin screw extruder. Other apparatus that may be employed includes a Buss Cokneader or Banbury mixer. Such formulation equipment may be preferred to an extruder where the graft reaction is to be performed and then the crosslinked polymer is to be stored for a period of time prior to manufacture.

Polymers as described above in the state fused to a silane having the general formula 1 described above.

The free radical generator is incorporated into the polymer to initiate the graft polymerization reaction.

Subjecting the composition thus produced to moisture, optionally at elevated temperature, will induce crosslinking of the silane groups via a combined hydrolysis and condensation reaction. Atmospheric humidity is usually sufficient to allow crosslinking to occur, but the crosslinking rate may be increased by the use of an artificially moistened atmosphere, or by immersion in liquid water. Also, subjecting the composition to combined heat and moisture will accelerate the crosslinking reaction. The crosslinking. Crosslinking can be carried out at a temperature above 50 ° C. In another embodiment, crosslinking is performed by exposing the composition to a temperature of about 85 ° C and a relative humidity of about 90% for approximately 100 hours.

Alternatively, it may be desirable to store the crosslinkable polymer of the present invention for some time prior to fabrication and crosslinking, so the hydrolysis / condensation catalyst should not be added during the production of the silane modified polymer. Instead, the condensation / hydrolysis catalyst should be mixed with the crosslinkable polymer in the manufacturing step.

The following non-limiting examples are also illustrative of the invention. EXAMPLES 1-2 These examples illustrate the preparation of diol-derived organofunctional silanes (designated Vinyl Silanes A and B, respectively), which will subsequently be grafted to the polyolefin followed by crosslinking of the grafted polyolefin.

Example 1: Preparation of Vinyl Silane A

Vinyl Silane A was prepared by the following method: 1,173.4 g (6.16 moles) of vinyltriethoxy silane (Sil-quest® A-151, available from GE Silicones) and 9.5 g of an ion exchange resin (Purolite CT-275 catalyst, available from Purolite Co., Inc.) were added to a 3 L round bottom flask equipped with an Oldershaw 5-plate distillation column, short-path distillation head, and addition funnel. . 728.3 g (6.16 mol) of hexylene glycol (available from Sigma-Aldrich Chemical Co.) was charged to the addition funnel. The contents of the flask were heated to about 50 ° C under vacuum to about 11,998.98 Pa (90 mmHg). The hexylene glycol was charged over a period of about 3 hours to the fraction. After the addition was complete, the vacuum was slowly decreased to maintain a constant distillation of ethanol. Distillation was continued until full vacuum and a crucible temperature of about 56 ° C were reached. The material was then allowed to cool for 12 hours and was filtered to remove Purolite catalyst. The material was then placed in a 2 L round bottom flask equipped with an Oldershaw five plate distillation column, and the remaining ethanol was removed under ambient pressure and a crucible temperature of about 80 ° C to yield approximately 1.097 g of Vinyl Silano A.

Example 2: Preparation of Vinyl Silane B

Vinyl Silane B was prepared by the following method: 633.8 g (2.22 moles) of vinyltriethoxy silane (Silquest® A-151, available from GE Silicones), 4.7 g of a sulfonated ion exchange resin ( Purolite CT-275 catalyst, available from Purolite Co., Inc.) and 300.0 g (2.22 moles) of 1,3-butanediol (available from Sigma-Aldrich Chemical Co.) were added to a round bottom flask. 3-liter unit equipped with an Oldershaw five-plate distillation column, short-path distillation head, and addition funnel. The contents of the flask were heated to about 40 ° C under vacuum at about 7,999.32 Pa (60 mmHg). The vacuum was slowly increased to maintain a constant distillation of ethanol. Distillation was continued until full vacuum and a crucible temperature of about 60 ° C were obtained. The material was then allowed to cool for about 12 hours and was filtered to yield approximately 536.0 g of Vinyl Silane B. EXAMPLES 3 AND 4: COMPARATIVE EXAMPLE 1 Examples 3 and 4 describe the preparation of compositions containing vinyl silane. based on vinyl Silane A (Example 1) and Vinyl Silane B (Example 2), respectively. Comparative Example 1, provided as a control, describes the preparation of a vinyl silane-based vinyltriethoxy silane-containing composition (Silquest® A-151).

Compositions containing vinyl silane were prepared by mixing each of the above silanes with the ingredients and in the amounts (grams) indicated in Table 1. All ingredients of the compositions were combined and stirred at room temperature in a glass vessel. , dry, closed until a homogeneous composition is obtained.

Table 1: Compositions Containing Vinyl Silane EXAMPLES 5-14; COMPARATIVE EXAMPLES 2-6 Examples 5 and 6 describe the absorption of vinyl silane-containing compositions of Examples 3 and 4, and Comparative Example 2 describes the absorption of the vinyl silane-containing composition of Comparative Example 1, in separate amounts of a carrier polymer. The carrier polymer was a porous high density polyethylene (HDPE) having a density of about 0.95 g / cm3. Each amount of the carrier polymer with its vinyl silane-containing composition absorbed therein was prepared by the following method: a dry, sealable glass vessel was filled to its capacity with the pellet carrier polymer. Next, a vinyl silane-containing composition was added at a weight ratio of 40:60 of the vinyl silane: carrier polymer composition. The vessel was then sealed and spun on motorized rubber rollers for about 25-30 minutes at room temperature, after which the vinyl silane-containing composition was completely absorbed into the carrier polymer. The pellets thus obtained (Examples 5 to 6 and Comparative Example 2) were stored in a dry atmosphere in a sealed container.

Examples 7-10 and 11-14 describe the preparation of physical mixtures including the pellets of Examples 5 to 6, respectively, and a high density polyethylene (HDPE) base polymer and Comparative Examples 3-6 describe the preparation. preparation of physical mixtures including the pellets of Comparative Example 2 and the HDPE base polymer. The HDPE base polymer used in these examples had a density of 0.944 g / cm3 and a melt flow of 3.5 g / 10 min at 190 ° C. Physical mixtures were prepared by the following method: The pellets and HDPE were loaded into a Maguire scale mixer in the amounts indicated in Table 2 and mixed. ______Table 2: Feeding Polymers to the Extruder________ EXAMPLES 15-22; COMPARATIVE EXAMPLES 7-10 These examples illustrate the silane graft for base polymer in physical mixtures of Examples 7-14 and Comparative Examples 3-6, above.

The physical mixtures of Examples 7-14 and Comparative Examples 3-6 were individually fed into a Hartig single screw extruder equipped with a 5.08 cm (2 inch) single screw with Length / Diameter ratio. (L / D) of 30: 1 / Maddox mixing head, and breaker plate containing 40, 60 and 80 mesh screen packs and extruded under the conditions shown below in Table 3, resulting in the silane grafting of each mixture into its component. HDPE. Each of the resulting extrudates was quenched in water, dried with a Berringer water separator and pelleted in a Cumberland pelletizer.

Table 3: Extrusion Conditions EXAMPLES 23-30; COMPARATIVE EXAMPLES 11-14 These examples illustrate the cross-linking of the HDPE component of the extrudates of Examples 15-22 and Comparative Examples 7-10 / above.

The silane grafted and pelleted HDPE extrudates of Examples 15-22 and Comparative Examples 7-10 were independently compression molded onto 15.24x15.24x0.0635 cm test plates. A representative portion of the plates were measured for percent gel content using Decaline extraction. To crosslink the silane grafted HDPE to each of the remaining plates, the plates were placed in a water bath at about 90 ° C for twelve hours. After crosslinking, the samples were minted on the crosslinked plates using a clicker and die press. Tensile strength, elongation and modulus at fracture were determined according to ASTM D-638 using a crosshead velocity of 0.0847 cm / s (2.0 inches / min) for all samples. The physical and mechanical properties of crosslinked samples are listed in Table 4 below.

Table 4: Physical Properties of Crosslinked Extrudates The percent gel content measured and tensile, elongation, and modulus results determined as per ASTM D-638 are shown in Figures 1-4. Figure 1 is a graph illustrating the percent gel content of the samples in Examples 23-30 and Comparative Examples 11-14. The gel content represents a measure of the degree of crosslinking in the sample, and by inference the degree of reaction of the silane. Comparative Examples 11-14, represented by Silquest® A-151 show a steady increase in gel content as silane content is increased. Examples 23-30 also show similar trends, with Examples 23-26, represented by Silane A, exhibiting a slightly higher gel content than Comparative Examples 11-14, at equivalent molar charge levels. Examples 27-30, represented by Silane B, have a slightly lower gel content compared to Comparative Examples 11-14 until the silane concentration of 2.0% is reached, at which point the gel content is equivalent. .

[00138] Figure 2 is a graph illustrating the tensile stress at break of Examples 23-30 and Comparative Examples 11-14. Examples 23-26, Silane A clearly show an advantage over Comparative Examples 11-14, Silquest® -151, at charge levels below and above about 1%. Examples 27-30, Silane B, exhibited slightly lower tensile stress values at the same load levels as Comparative Examples 11-14.

Figure 3 is a graph illustrating the percent elongation at break for Examples 23-26 and Comparative Examples 11-14. Examples 23-26, Silane A, show a greater elongation than Comparative Examples 1114, Silguest® A-151, at eguivalent load levels below and above 1.5%. Examples 27-30, Silane B, exhibit lower elongation than Comparative Examples 11-14.

Figure 4 is a graph illustrating the modulus of rupture of the compounds produced in Examples 23-30 and Comparative Examples 11-14. Examples 23-26, Silane A, have a performance equivalent to Comparative Examples 11-14, Silguest® A-151, except at higher loads of 2%, where Examples 23-26, Silane A, show some improvement. Examples 27-30, Silane B, show a significantly increased modulus versus Comparative Examples at higher charge levels than 0.5%.

In general, the silanes of the present invention show equivalent or improved performance compared to currently employed silanes, and offer significant benefit by reducing the amount of volatile organic compounds that are released.

Although the invention has been described with reference to various exemplary embodiments, it will be understood by those skilled in the art that various modifications may be made and equivalents may be used in their place without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention be not limited to any particular exemplary embodiment described herein.

Claims (12)

Process for cross-linking Polymer Characteristic comprising: (a) introducing into the structure of the thermoplastic polymer to be cross-linked, under substantially anhydrous conditions, a silane of the formula: [Y [-G (-SiXuZbvZcw) s] r] n (Formula 1) wherein: each occurrence of G is independently selected from a group of groups consisting of a polyvalent group derived by substitution of one or more hydrogen atoms of an alkyl, alkenyl, aryl and aralkyl group; and a molecular component which may be obtained by removing one or more hydrogen atoms from a heterocarbon, with G containing from 1 to 30 carbon atoms; each occurrence of X is independently selected from the group consisting of -Cl, -Br, R10-, R1C (= 0) 0-, R1R2C = NO—, R1R2NO- or R1R2N-, -R1, - (OSiRiR2) t (OSiR1R2R3) ), and - O (R10CR1; L) fOH, wherein each occurrence of R1, R2, R3, R10 and R11 is independently R; each occurrence of Zb is independently (-0-) o, 5, and [-0 (R10CR1: L) fO-] 0.5, where each occurrence of R10 and R11 is independently R; each occurrence of Zc is independently given by -O (R10CR1; L) fO-, where each occurrence of R10 and R11 is independently R; each occurrence of R is independently selected from the group of groups consisting of hydrogen; straight chain, cyclic and branched alkyl groups, alkenyl groups, aryl groups and aralkyl groups containing from 1 to 20 carbon atoms; and molecular components obtained by removing one or more hydrogen atoms from a hetero carbon containing from 1 to 20 carbon atoms; each occurrence of the subscript f is an integer from 1 to 15; each occurrence of n is an integer from 1 to 100, with the proviso that when n is greater than 1, v is greater than 0 and all valencies for Zb have a silicon atom attached thereto; each occurrence of the subscript u is an integer from 0 to 3; each occurrence of subscript v is an integer from 0 to 3; each occurrence of subscript w is an integer from 0 to 1, with the proviso that u + v + 2w = 3, each occurrence of subscript r is an integer from 1 to 6, each occurrence of subscript t is an integer from 0 to 50; each occurrence of the subscript s is an integer from 1 to 6; and each occurrence of Y is a univalent, bivalent, trivalent, tetravalent or multi-lens valence r-organofunctional group, wherein: the univalent organofunctional group is selected from the group consisting of CH2 = CH-, CHR = CH-, CR2 = CH-, mercapto, acryloxy, methacryloxy, acetoxy, O-CH2-C2H3O, -CH2-CH2-C6H90, -C6H90, -CR6 (-0-) CR4R5, -OH, -NR4C (= 0) OR5, - OC (= 0) NR4R5, -NR4C (= 0) SR5, -SC (= 0) NR4R5, -NR4C (= S) OR5, - OC (= S) NR4R5, -NR4C (= S) SR5, -SC ( = S) NR 4 R 5, maleimide, maleate, substituted maleate, fumarate, substituted fumarate, -CN, citraconimide, -OCN, -N = C = 0, -SCN, -N = C = S, -OR4, -F, -Cl , -Br; -I, -SR4, -S-SR4, -SS-SR4, -SSS-SR4, -SSSS-SR4, -SSSSS-SR4, -SxR4, -SC (= S) OR4, -SC (= S) SR4, -SC (= 0) SR4, - NR4C (= 0) NR5R6, -NR4C (= S) NR5R6, R4C (= 0) NR5-, -C (= 0) NR4R5-, R4C (= S) NR4, melamine, cyanurate, -NH2, -NHR4, -NR4R5, -NR4-L1-NR5R6, -NR4-L1 (-NR5R6) 2, -NR4-L1-NR5-L2-NR6R7, -NR4-L1 (NR5R6) 3, —NR4 —L1 — NR5 — L2 — NR6 — L3 — NR7R8 and -NR4-L1-N (-L2NR5R6) 2; the divalent organofunctional group is selected from the group consisting of - (-) C (-0-) CR4R5, -CR5 (-0-) CR4-, - OtR ^ CRUjfO-, - (-) NC (= 0) OR5, -0C (= 0) NR4-, - (-) NC (= 0) SR5, - SC (= 0) NR4—, - (-) NC (= S) OR5, -0C (= S) NR4-, - (-) NC (= S) SR5, - SC (= S) NR4 -, -0-, maleate, substituted maleate, fumarate, substituted fumarate, -S-, -SS-, -SSS-, -SSSS-, - SSS-SS-, -SSSSSS-, -Sx-, -SC (= S) 0-, -SC (= S) S-, -SC (= 0) S-, - (-) NC (= 0) NR4R5 , —NR4C (= 0) NR5—, - (-) NC (= S) NR4R5, -NR4C (= S) NR5-, R4C (= 0) N (-) -, —C (= 0) NR4—, R4C (= S) N (-) -, divalent melamine, bivalent cyanurate, -NH-, -NR4-, - (-) N-L1-NR4R5, NR4-L1-NR5-, (-) NR4) 2 — L1 —NR5R6, - (-) N-L1-NR5-L2-NR6R7, -NR4-L1-N (-) -L2-NR5R6, -NR4-L1-NR5-L2-NR6-, - (-) N-L1 - (NR5R6) 3, (-NR4) 2-L1- (NR5R6) 2, - (-) N-L1-NR4-L2-NR5-L3-NR6R7, -NR4-L4-N (-) -L2-NR5 -L3-NR6R7, -NR4-L1-NR5-L2-N (-) -L3-NR6R7, -NR4-L1-NR5-L2-NR6-L3-NR7-, - (-) N-L1-N (- L2NR5R6) 2 and (-NR4L1-) 2N-L2NR5R6; the trivalent organofunctional group is selected from the group consisting of - (-) C (-0-) CR4-, - (-) NC (= 0) 0, - (-) NC (= 0) S-, - (- ) NC (= S) 0-, - (-) NC (= S) S-, - (-) NC (= 0) NR4-, - (-) NC (= S) NR4—, -C (= 0 ) N (-) -, -C (= S) N (-) -, trivalent melamino; trivalent cyanurate, -N (-) -, - (-) N-L1-NR4-, (-NR4) 3-L1, (-NR4) 2-L1-NR5-, - (-) Ν-ΐΛ-Ν ( -) - L2-NR3R4, -NR4-L1-N (-) - L2-NR5-, - (-) N-L1-NR4-L2-NR5—, - (-) Ν-ΐΛ-Ν (-) - L2-NR5-L3-NR3R4, -NR4-L1-N (-) - L2-N (-) -L3-NR3R4, - (-) N-L1-NR5-L2-N (-) -L3-NR3R4, -NR4-L1-N (-) - L2-NR3-L3-NR4-, - (-) N-L1-N (-L2NR3R4) (-L2NR5-) and (-NR4L1-) 3N; the tetravalent organofunctional group is selected from the group consisting of - (-) C (-0-) C (-) -, - (-) NC (= 0) N (-) -, - (-) NC (= S ) N (-) -, tetravalent melamine, - (-) N-L1-N (-) -, (- NR4) 4-L1, (-NR4) 2-L1-N (-) -, - (-) N-L1-N (-) -L2-NR3-, - (-) N-L1-NR4-L2 (-) -, - (-) N-L1-N (-) -L2-N (-) - L3-NR4R3, -NR4-L1-N (-) - L2-N (-) —L3-NR3-, - (-) N-L1-NR4-L2-NR3-L3-N (-) - and - ( -) N-L1-N (-L2NR3-) 2; and the polyvalent organofunctional group is selected from the group consisting of polyvalent hydrocarbon groups, (-NR3) (-N-) 2C3N3, (-N-) 3C3N3, - (-) N-L4-N (-) -L2 -N (-) -, - (-) N-L1-N (-) -L2-N (-) -L3-NR3-, - (-) N-L1-NR3-L2-N (-) -L3 -N (-) -, [- (-) N — L1—] 2N — L2NR3—, - (-) N — L1 — N (-) -L2 — N (-) - L3 — N (-) - and [- (-) N-14-] 3, where each occurrence of L1, L2 and L3 is selected independently of the set of structures given above for G, each occurrence of R3, R4, R5, R6, R7, R8, R10 and R11 is independently given by one of the structures listed above for R ex is independently an integer from 1 to 10; provided that the silane of Formula (1) contains at least one occurrence of Zc and that upon hydrolysis of its hydrolysable sites produces a reduced amount of volatile organic compound compared to that produced by hydrolysis of a silane having a number equivalent of hydrolysable sites, all of which are hydrolysable alkoxy groups; and b) cross-linking the polymer by exposing the polymer to hydrolysis / condensation conditions. Process according to Claim 1, characterized in that the polymer is selected from the group consisting of a homopolymer of polyethylene, polypropylene, polybutadiene, high density polyethylene, low density polyethylene, linear low density polyethylene, vinyl polychloride, vinylidene polychloride, chlorinated polyethylene; a copolymer derived from two or more of ethylene, propylene, butene, pentene, hexene, heptene, octane, nonene and decene; copolymer selected from the group consisting of ethylene copolymerized with one or more other ethylenically unsaturated moiety, ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid ester and ethylenically unsaturated dicarboxylic acid anhydride; ethylene propylene rubber (EP) olefin based rubber, ethylene propylene diene monomer rubber (EDPM) and styrene butadiene rubber (SRB); and ionomer resin. Process according to Claim 1, characterized in that one of the following (a) - (i): (a) Y is a univalent organofunctional; or (b) G is selected from the group consisting of diethylene cyclohexane, 1,2,4-triethylene cyclohexane, diethylene benzene, phenylene, - (CH 2) m-, where m is 1 to 12 and CH 2 ( CH 2) q CH (CH 3) wherein q is zero to 17; or (c) R, R1, R2, R3, R4, R5, R6, R7, R8, R10 and R11 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, octenyl, cyclohexyl, butyl phenyl, benzyl, tolyl, allyl, methoxyethyl, ethoxyethyl, dimethylaminoethyl and cyanoethyl; or (d) R10 and R11 are each independently selected from the group consisting of hydrogen, methyl and ethyl; or (e) R1 and R2 are independently selected from the group consisting of hydrogen, methyl, ethyl and propyl; or (f) R3, R4, R5, R6, R7 and R8 are independently selected from the group consisting of phenyl, methyl, butyl, H and ethyl; or (q) X is selected from the group consisting of methoxy, ethoxy, isobutoxy, propoxy, isopropoxy, acetoxy, methoxyethoxy, oximate and monovalent dioxy-derived alkoxy groups; or (h) Zb and Zc are selected from the group consisting of divalent alkoxy groups derived from diols consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3 -butanediol and 2-methyl-2,4-pentanediol; or (i) v is 0, X is RO- or RC (= 0) -, R is a C1 to C4 alkyl or H, and G is a straight chain bivalent alkyl of 2 to 18 carbon atoms. Process according to Claim 1, characterized in that the univalent organofunctional group is selected from the group consisting of CH2 = CH-, CHR = CH-, CR2 = CH-, mercapto, acryloxy, methacryloxy, acetoxy, O-CH 2 -C 2 H 3 O, -CH 2 -CH 2 -C 6 H 9 O, maleimide, maleate, substituted maleate, fumarate, -CN, -N = C = 0, -Cl, —NR 4 C (= 0) NR 5 R 6, -NH 2, -NHR 4 and -NR4R5; the divalent organofunctional group is selected from the group consisting of -S-S-, -S-S-S-, -S-S-S-S-, -S-S-S-S-S, -S-S-S-S-S-, -Sx-, -NH-, -NR4-; the organofunctional trivalent group is selected from the group consisting of trivalent melamino and trivalent cyanurate; wherein each occurrence of R 4, R 5 and R 6 is independently R, wherein R is independently selected from the group of groups consisting of hydrogen; alkyl groups, alkenyl groups, aryl groups and straight chain, cyclic and branched aralkyl groups having from 1 to 20 carbon atoms; and molecular components obtained by removing one or more hydrogen atoms from a heterocarbon containing from 1 to 20 carbon atoms; and x is independently an integer from 1 to 10. A process according to claim 4, characterized in that the dialkoxy group Zc is represented by the formula: wherein R 10 and R 11 are each independently selected from one or more. group consisting of hydrogen, methyl and ethyl. Process according to Claim 1, characterized in that step (a) of the process for introducing a silane into the structure of a thermoplastic polymer comprises: A) combining under substantially moisture-free conditions: (i) thermoplastic base polymer; (ii) solid carrier polymer; (iii) hydrolyzable silane of the formula: wherein each occurrence of G is independently selected from a group of groups consisting of a polyvalent group derived from: (Y) -G (-SiXuZbvZcw) s] r] n. substitution of one or more hydrogen atoms of an alkyl, alkenyl, aryl and aralkyl group; and a molecular component which may be obtained by removing one or more hydrogen atoms from a heterocarbon, with G containing from 1 to 30 carbon atoms; each occurrence of X is independently selected from the group consisting of -Cl, -Br, R10-, R1C (= 0) 0-, R1R2C = NO—, R1R2NO- or R1R2N-, -R1, - (OSiRiR2) t (OSiR1R2R3) ), and - O (R10CR1; L) fOH, wherein each occurrence of R1, R2, R3, R10 and R11 is independently R; each occurrence of Zb is independently (-0-) o, 5, and [-0 (R10CR1: L) fO-] 0.5, where each occurrence of R10 and R11 is independently R; each occurrence of Zc is independently given by -0 (R10CR1; 1) fO-, where each occurrence of R10 and R11 is independently R; each occurrence of R is independently selected from the group of groups consisting of hydrogen; alkyl groups, alkenyl groups, aryl groups and straight chain, cyclic and branched aralkyl groups having from 1 to 20 carbon atoms; and molecular components obtained by removing one or more hydrogen atoms from a heterocarbon containing from 1 to 20 carbon atoms; each occurrence of subscript f is an integer from 1 to 15, each occurrence of n is an integer from 1 to 100, with the proviso that when n is greater than 1, v is greater than 0, and all valences for Zb have a silicon atom bonded to them; each occurrence of the subscript u is an integer from 0 to 3; each occurrence of subscript v is an integer from 0 to 3; each occurrence of subscript w is an integer from 0 to 1, with the proviso that u + v + 2w = 3} each occurrence of subscript r is an integer from 1 to 6; each occurrence of the subscript t is an integer from 0 to 50; each occurrence of the subscript s is an integer from 1 to 6; and each occurrence of Y is selected from the group consisting of CH2 = CH-, CHR = CH-, CR.2 = CH-, mercapto, acryloxy, methacryloxy, provided that the silane of Formula! contains at least one occurrence of Zc, (iv) a free radical generator, and optionally (v) catalyst for silane hydrolysis / condensation reactions (iii) when silane (iii) is exposed to moisture; B) heating the resulting combination from step (A) to a temperature above the crystalline melting point of the base polymer (i) to graft silane (iii) into the base polymer (i). A process according to claim 6, characterized in that one of the following (i) - (viii): (i) step (A) is conducted by: al) combining the carrier polymer (ii), silane (iii) and free radical generator (iv) to provide a premix in which silane (iii) and free radical generator (iv) are incorporated into the carrier polymer (ü); and a2) combining the premix resulting from step (al) with the base polymer (i), optionally with catalyst (v); or (ii) the carrier polymer (ii) represents from 0.01 to 40% by weight of the combined weight of the base polymer (i) and the carrier polymer (ii); or (iii) the carrier polymer (ii) represents from 0.01 to 20% by weight of the combined weight of the base polymer (i) and the carrier polymer (ii); or (iv) the thermoplastic base polymer (i) is selected from the group consisting of homopolymers and copolymers of ethylene, propylene, butene, pentene, hexene, heptene, octane, nonene and decene; or (v) the carrier polymer (ii) is selected from the group consisting of ethylene vinyl acetate (EVA) copolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, a an alpha olefin monopolymer having from 2 to 6 carbon atoms and a two alpha olefin copolymer; or (vi) silane (iii) has the general formula: [Y [-G (-SiXuZbvZcw) s] r] n (Formula 1) wherein: each occurrence of G is independently selected from a group of groups comprising a polyvalent group derived by substitution of one or more hydrogen atoms of an alkyl, alkenyl, aryl and aralkyl group; and a molecular component which may be obtained by removing one or more hydrogen atoms from a heterocarbon, with G containing from 1 to 30 carbon atoms; each occurrence of X is independently selected from the group consisting of R10- and -O (R10CR1; L) fOH, where each occurrence of R1, R10 and R11 is independently R; each occurrence of Zb is independently (-0-) o, 5, and [-0 (R10CR1: L) fO-] 0.5, where each occurrence of R10 and R11 is independently R; each occurrence of Zc is independently given by -0 (R10CR1; 1) fO-, where each occurrence of R10 and R11 is independently R; each occurrence of R is independently selected from the group of groups comprising hydrogen; alkyl groups alkenyl groups, aryl groups and straight chain, cyclic or branched aralkyl groups having from 1 to 20 carbon atoms; and molecular components obtained by removing one or more hydrogen atoms from a heterocarbon containing from 1 to 20 carbon atoms; each occurrence of the subscript f is an integer from 1 to 15; each occurrence of n is an integer from 1 to 100, with the proviso that when n is greater than 1, v is greater than 0 and all valencies for Zb have a silicon atom attached thereto; each occurrence of the subscript u is an integer from 0 to 3; each occurrence of subscript v is an integer from 0 to 3; each occurrence of subscript w is an integer from 0 to 1, with the proviso that u + v + 2w = 3} each occurrence of subscript r is an integer from 1 to 6; each occurrence of the subscript t is an integer from 0 to 50; each occurrence of the subscript s is an integer from 1 to 6; and each occurrence of Y is selected from the group consisting of CH2 = CH-, CHR = CH-, CR.2 = CH-, acryloxy and methacryloxy-with the proviso that each silane of Formula (1) contains at least an occurrence of Zc; or (vii) the free radical generator (iv) is selected from the group consisting of organic peroxides, azo compounds and peresters; or (viii) the optional catalyst (v) is selected from the group consisting of dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin octanoate, dioctyl maleate, dibutyl tin oxide, titanium-2-ethylhexoxide and any combination of these. Process according to Claim 7, characterized in that in step (al), silane (iii) and free radical generator (iv) are combined, the resulting combination is thereafter combined with the carrier polymer (ii) to provide the premix; or in step (a2), the base polymer (i) and catalyst (v) are combined, the resulting combination is thereafter combined with the resulting premix of step (al). A process according to claim 7, characterized in that in step (a2) the base polymer (i) and catalyst (v) are combined, the resulting combination is thereafter combined with resulting mixture from step (al). Process according to claim 7, characterized in that in part (vi) one of the following (a) - (g): (a) Y is selected from the group consisting of CH 2 = CH- and methacryloxy; or (b) G is selected from the group consisting of diethylene cyclohexane, 1,2,4-triethylene cyclohexane, diethylene benzene, phenylene, - (CH 2) m-, where m is 1 to 12 and CH 2 (CH 2) qCH (CH3) wherein q is zero to 17; or (c) R, R1, R10 and R11 are independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, octenyl, cyclohexyl, butyl, phenyl, benzyl, to-lila, allyl, methoxyethyl, ethoxyethyl, dimethylaminoethyl and cyanoethyl; or (d) R10 and R11 are each independently selected from the group consisting of hydrogen, methyl and ethyl; or (e) R1 is selected from the group consisting of hydrogen, methyl, ethyl and propyl; or (f) X is selected from the group consisting of methoxy, ethoxy, isobutoxy, propoxy, isopropoxy; or (g) Zb and Zc are selected from the group consisting of bivalent alkoxy groups derived from diols consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3 -butanediol and 2-methyl-2,4-pentanediol. Process according to claim 10, characterized in that in part (a), the univalent organo-functional group is CH 2 = CH-. A cross-linked polymer characterized by being prepared by the process as defined in claim 1, wherein the polymer is produced by the process comprising introducing into the structure of the thermoplastic polymer to be cross-linked, under substantially anhydrous conditions, a silane of the formula: [Y [-G (-SiXuZbvZcw) s] r] n (Formula 1) wherein: each occurrence of G is independently selected from a group of groups consisting of a polyvalent group derived by substitution of one or more hydrogen atoms of an alkyl, alkenyl, aryl and aralkyl group; and a molecular component which may be obtained by removing one or more hydrogen atoms from a heterocarbon with G containing from 1 to 30 carbon atoms; each occurrence of X is independently selected from the group consisting of -Cl, -Br, R10-, R1C (= 0) 0-, R1R2C = NO—, R1R2NO- or R1R2N-, -R1, - (OSiRiR2) t (OSiR1R2R3) ), and - O (R10CR1; L) fOH, wherein each occurrence of R1, R2, R3, R10 and R11 is independently R; each occurrence of Zb is independently (-0-) o, 5, and [-0 (R10CR1: L) fO-] 0.5, where each occurrence of R10 and R11 is independently R; each occurrence of Zc is independently given by -O (R10CR1; L) fO-, where each occurrence of R10 and R11 is independently R; each occurrence of R is independently selected from the set of groups consisting of hydrogen; alkyl groups, alkenyl groups, aryl groups and straight chain, cyclic and branched aralkyl groups having from 1 to 20 carbon atoms; and molecular components obtained by removing one or more hydrogen atoms from a heterocarbon containing from 1 to 20 carbon atoms; each occurrence of the subscript f is an integer from 1 to 15; each occurrence of n is an integer from 1 to 100, with the proviso that when n is greater than 1, v is greater than 0 and all valencies for Zb have a silicon atom attached thereto; each occurrence of the subscript u is an integer from 0 to 3; each occurrence of subscript v is an integer from 0 to 3; each occurrence of subscript w is an integer from 0 to 1, with the proviso that u + v + 2w = 3, each occurrence of subscript r is an integer from 1 to 6, each occurrence of subscript t is an integer from 0 to 50; each occurrence of the subscript s is an integer from 1 to 6; and each occurrence of Y is a univalent, bivalent, trivalent, tetravalent or multi-lens valence r-organofunctional group, wherein: the univalent organofunctional group is selected from the group consisting of CH2 = CH-, CHR = CH-, CR2 = CH-, mercapto, acryloxy, methacryloxy, acetoxy, O-CH2-C2H3O, -CH2-CH2-C6H90, -C6H90, -CR6 (-0-) CR4R5, -OH, -NR4C (= 0) OR5, - OC (= 0) NR4R5, -NR4C (= 0) SR5, -SC (= 0) NR4R5, -NR4C (= S) OR5, -OC (= S) NR4R5, -NR4C (= S) SR5, -SC ( = S) NR 4 R 5, maleimide, maleate, substituted maleate, fumarate, substituted fumarate, -CN, citraconimide, -OCN, -N = C = 0, -SCN, -N = C = S, -OR4, -F, -Cl , -Br; -I, -SR4, -S-SR4, -SS-SR4, -SSS-SR4, -SSSS-SR4, -SSSSS-SR4, -SxR4, -SC (= S) OR4, -SC (= S) SR4, -SC (= 0) SR4, - NR4C (= 0) NR5R6, -NR4C (= S) NR5R6, R4C (= 0) NR5-, -C (= 0) NR4R5-, R4C (= S) NR4, melamine, cyanurate, -NH2, -NHR4, -NR4R5, -NR4-L1-NR5R6, -NR4-L1 (-NR5R6) 2, -NR4-L1-NR5-L2-NR6R7, -NR4-L1 (NR5R6) 3, —NR4 —L1 — NR5 — L2 — NR6 — L3 — NR7R8 and -NR4-L1-N (-L2NR5R6) 2; the bivalent organofunctional group is selected from the group consisting of - (-) C (-0-) CR4R5, -CR5 (-0-) CR4-, - OtR ^ CRUjfO-, - (-) NC (= 0) OR5, -0C (= 0) NR4-, - (-) NC (= 0) SR5, -SC (= 0) NR4-, - (-) NC (= S) OR5, -0C (= S) NR4-, - (-) NC (= S) SR5, - SC (= S) NR4 -, -0-, maleate, substituted maleate, fumarate, substituted fumarate, -S-, -SS-, -SSS-, -SSSS-, - SSS-SS-, -SSSSSS-, -Sx-, -SC (= S) 0-, -SC (= S) S-, -SC (= 0) S-, - (-) NC (= 0) NR4R5 , —NR4C (= 0) NR5—, - (-) NC (= S) NR4R5, -NR4C (= S) NR5-, R4C (= 0) N (-) -, —C (= 0) NR4—, R4C (= S) N (-) -, divalent melamine, bivalent cyanurate, -NH-, -NR4-, - (-) N-L1-NR4R5, NR4-L1-NR5-, (-) NR4) 2 — L1 —NR5R6, - (-) N-L1-NR5-L2-NR6R7, -NR4-L1-N (-) -L2-NR5R6, -NR4-L1-NR5-L2-NR6-, - (-) N-L1 - (NR5R6) 3, (-NR4) 2-L1- (NR5R6) 2, - (-) N-L1-NR4-L2-NR5-L3-NR6R7, -NR4-L4-N (-) -L2-NR5 -L3-NR6R7, -NR4-L1-NR5-L2-N (-) -L3-NR6R7, -NR4-L1-NR5-L2-NR6-L3-NR7-, - (-) N-L1-N (- L2NR5R6) 2 and (-NR4L1-) 2N-L2NR5R6; the trivalent organofunctional group is selected from the group consisting of - (-) C (-0-) CR4-, - (-) NC (= 0) 0, - (-) NC (= 0) S-, - (- ) NC (= S) 0-, - (-) NC (= S) S-, - (-) NC (= 0) NR4-, - (-) NC (= S) NR4—, -C (= 0 ) N (-) -, -C (= S) N (-) -, trivalent melamino; trivalent cyanurate, -N (-) -, - (-) N-L1-NR4-, (-NR4) 3-L1, (-NR4) 2-L1-NR5-, - (-) Ν-ΐΛ-Ν ( -) - L2-NR3R4, -NR4-L1-N (-) - L2-NR5-, - (-) N-L1-NR4-L2-NR5—, - (-) N-La-N (-) - L2-NR5-L3-NR3R4, -NR4-L1-N (-) - L2-N (-) -L3-NR3R4, - (-) N-L1-NR5-L2-N (-) -L3-NR3R4, -NR4-L1-N (-) - L2-NR3-L3-NR4-, - (-) N-L1-N (-L2NR3R4) (-L2NR5-) and (-NR4L1-) 3N; the tetravalent organofunctional group is selected from the group consisting of - (-) C (-0-) C (-) -, - (-) NC (= 0) N (-) -, - (-) NC (= S ) N (-) -, tetravalent melamine, - (-) N-L1-N (-) -, (- NR4) 4-L1, (-NR4) 2-L1-N (-) -, - (-) N-L1-N (-) -L2-NR3-, - (-) N-L1-NR4-L2 (-) -, - (-) N-L1-N (-) -L2-N (-) - L3-NR4R3, -NR4-L1-N (-) - L2-N (-) —L3-NR3-, - (-) N-L1-NR4-L2-NR3-L3-N (-) - and - ( -) N-L1-N (-L2NR3-) 2; and the polyvalent organofunctional group is selected from the group consisting of polyvalent hydrocarbon groups, (-NR3) (-N-) 2C3N3, (-N-) 3C3N3, - (-) N-L4-N (-) -L2 -N (-) -, - (-) N-L1-N (-) -L2-N (-) -L3-NR3-, - (-) N-L1-NR3-L2-N (-) - L3 -N (-) -, [- (-) N — L1—] 2N — L2NR3—, - (-) N — L1 — N (-) -L2 — N (-) - L3 — N (-) - and [- (-) N-14-] 3, where each occurrence of L1, L2 and L3 is selected independently of the set of structures given above for G, each occurrence of R3, R4, R5, R6, R7, R8, R10 and R11 is independently given by one of the structures listed above for R ex is independently an integer from 1 to 10; provided that the silane of Formula (1) contains at least one occurrence of Zc and that upon hydrolysis of its hydrolysable sites produces a reduced amount of volatile organic compound compared to that produced by hydrolysis of a silane having a number equivalent of hydrolysable sites, all of which are hydrolysable alkoxy groups.